21 applications analytical -biosensors - environmental 2012

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Autolab Instruments in Environmental Research

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Page 1: 21   applications analytical -biosensors - environmental 2012

Autolab Instruments in Environmental Research

Environmental applications

bull Determination of Heavy metals

bull Determination of organics pollution elements

bull Preparations of Sensors biosensors imunosensors

bull Preparation of electronic tongue EQCM

bull Electrochemical elimination of contaminants

We found 8366 Articles

Using Autolab equipments on environmental applications

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Differential pulse voltammetry bull Square wave voltammetry bull Cyclic Voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections bull Electrochemical Impedance Spectroscopy bull (Electrochemical Surface Plasmon Resonance)

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Mercury Electrode bull Solid state electrode Graphite Platinum bull Special depositionmodification electrodes bull Screen printed electrodes

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors bull Screen print electrodes bull self assembled monolayer

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 2: 21   applications analytical -biosensors - environmental 2012

Environmental applications

bull Determination of Heavy metals

bull Determination of organics pollution elements

bull Preparations of Sensors biosensors imunosensors

bull Preparation of electronic tongue EQCM

bull Electrochemical elimination of contaminants

We found 8366 Articles

Using Autolab equipments on environmental applications

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Differential pulse voltammetry bull Square wave voltammetry bull Cyclic Voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections bull Electrochemical Impedance Spectroscopy bull (Electrochemical Surface Plasmon Resonance)

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Mercury Electrode bull Solid state electrode Graphite Platinum bull Special depositionmodification electrodes bull Screen printed electrodes

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors bull Screen print electrodes bull self assembled monolayer

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 3: 21   applications analytical -biosensors - environmental 2012

We found 8366 Articles

Using Autolab equipments on environmental applications

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Differential pulse voltammetry bull Square wave voltammetry bull Cyclic Voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections bull Electrochemical Impedance Spectroscopy bull (Electrochemical Surface Plasmon Resonance)

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Mercury Electrode bull Solid state electrode Graphite Platinum bull Special depositionmodification electrodes bull Screen printed electrodes

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors bull Screen print electrodes bull self assembled monolayer

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 4: 21   applications analytical -biosensors - environmental 2012

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Differential pulse voltammetry bull Square wave voltammetry bull Cyclic Voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections bull Electrochemical Impedance Spectroscopy bull (Electrochemical Surface Plasmon Resonance)

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Mercury Electrode bull Solid state electrode Graphite Platinum bull Special depositionmodification electrodes bull Screen printed electrodes

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors bull Screen print electrodes bull self assembled monolayer

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 5: 21   applications analytical -biosensors - environmental 2012

bull Differential pulse voltammetry bull Square wave voltammetry bull Cyclic Voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections bull Electrochemical Impedance Spectroscopy bull (Electrochemical Surface Plasmon Resonance)

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Mercury Electrode bull Solid state electrode Graphite Platinum bull Special depositionmodification electrodes bull Screen printed electrodes

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors bull Screen print electrodes bull self assembled monolayer

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 6: 21   applications analytical -biosensors - environmental 2012

bull Mercury Electrode bull Solid state electrode Graphite Platinum bull Special depositionmodification electrodes bull Screen printed electrodes

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors bull Screen print electrodes bull self assembled monolayer

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 7: 21   applications analytical -biosensors - environmental 2012

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors bull Screen print electrodes bull self assembled monolayer

Environmental applications

Methods Electrodes

Development

Imunosensors Biosensors

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 8: 21   applications analytical -biosensors - environmental 2012

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Electrochemical Techniques

Environmental applications

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 9: 21   applications analytical -biosensors - environmental 2012

Hardware

NON MODULAR INSTRUMENT

MODULAR INSTRUMENTS

PGSTAT 101 Autolab Type IIIFRA2

PGSTAT302N PGSTAT128N PGSTAT100

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 10: 21   applications analytical -biosensors - environmental 2012

- Software -

Cyclic Voltammetry Linear sweep voltammetry Differential pulse voltammetry Square wave voltammetry Direct current voltammetry Normal pulse voltammetry Differential normal pulse voltammetry Chrono methods Electrochemical noise Impedance techniques

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 11: 21   applications analytical -biosensors - environmental 2012

- Software -

FRA

GPES

All includes in NOVA

Alternative current voltammetry Potentiometric stripping analysis Multimode electrochemical detection

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 12: 21   applications analytical -biosensors - environmental 2012

Voltammetric Analysis

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 13: 21   applications analytical -biosensors - environmental 2012

SMDE

Stable surface

Needle

Capillary

Tapper

Hg drop

DME

Droplife

New Drop

Electrode types in Voltammetric Analysis

Voltammetric Analysis

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 14: 21   applications analytical -biosensors - environmental 2012

Electrode types in Voltammetric Analysis

MME Multi Mode Electrode

SMDE DME HMDE

GC Au Ag Pt UT

RDE Rotating Disc Electrode

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 15: 21   applications analytical -biosensors - environmental 2012

Multi Mode Electrode

Precise and safe control of the Hg drop electrode

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 16: 21   applications analytical -biosensors - environmental 2012

Multi Mode Electrode

bull Hg drop

ndashDME

ndashSMDE

ndashHDME

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 17: 21   applications analytical -biosensors - environmental 2012

Possibility of determinations with DP and SQW

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 18: 21   applications analytical -biosensors - environmental 2012

bull Sb 500 ppt

bull As 100 ppt

bull Pb 10 ppt

bull Cd 10 ppt

bull Cr 25 ppt

bull Fe 200 ppt

bull Co 50 ppt

bull Cu 50 ppt

bull Rh 01 ppt

bull Hg 100 ppt

bull Mo 10 ppt

bull Ni 50 ppt

bull Pt 01 ppt

bull Tl 50 ppt

bull U 25 ppt

bull Bi 500 ppt

bull Se 300 ppt

bull W 200 ppt

Possibility of determinations with DP and SQW

Ultra trace analysis

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 19: 21   applications analytical -biosensors - environmental 2012

Normal Pulse Voltammetry

Voltammetric Analysis

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 20: 21   applications analytical -biosensors - environmental 2012

Normal Pulse Voltammetry

bull Dropping Mercury Electrode (DME) Improved sensitivity compared to classical DC polarography bull Static Mercury Drop Electrode (SMDE) No charging current --gt lower background current No slope in background current --gt Improved precision Smaller drop times --gt faster measurements

Voltammetric Analysis

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 21: 21   applications analytical -biosensors - environmental 2012

Normal Pulse Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 22: 21   applications analytical -biosensors - environmental 2012

Differential pulse voltammetry (DPV)

Voltammetric Analysis

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 23: 21   applications analytical -biosensors - environmental 2012

Differential pulse voltammetry current measurement

Current is the difference between 2 and 1

Voltammetric Analysis

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 24: 21   applications analytical -biosensors - environmental 2012

W12

E0

Differential pulse voltammetry

Voltammetric Analysis

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 25: 21   applications analytical -biosensors - environmental 2012

Differential pulse voltammetry

bull Currents will only be measured close to E0

bull Wfrac12 = 904n mV if the pulse height is small

bull Advantages over Normal Pulse Voltammetry

1 Cancellation of capacitive currents 2 Ability to distinguish closeoverlapping peaks 3 Higher currents and higher selectivity

Voltammetric Analysis

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 26: 21   applications analytical -biosensors - environmental 2012

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 27: 21   applications analytical -biosensors - environmental 2012

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 28: 21   applications analytical -biosensors - environmental 2012

Differential pulse voltammetry Voltammetric Analysis

measurement in acetateKCl solution pH=49

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 29: 21   applications analytical -biosensors - environmental 2012

Square Wave Voltammetry

Square wave is applied on top of a DC scan

Voltammetric Analysis

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 30: 21   applications analytical -biosensors - environmental 2012

Square wave voltammetry Measurement

bullThe displayed result is the difference between

a forward and backward current

bullIforward and Ibackward can be saved as well

bullSquare wave period 05 ms ndash 125 ms

(f8 Hz-2000 Hz)

Voltammetric Analysis

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 31: 21   applications analytical -biosensors - environmental 2012

Square Wave Voltammetry The best choice for analytical purposes

bull Background current cancellation (same as DPV)

bull Slightly more sensitive than DPV

bull Faster scan rates

bull Less Hg consumed

Voltammetric Analysis

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 32: 21   applications analytical -biosensors - environmental 2012

Square Wave Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 33: 21   applications analytical -biosensors - environmental 2012

SQW Voltammetry DP Voltammetry

Cd2+ measurement in acetateKCl solution pH=49

Voltammetric Analysis comparison

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 34: 21   applications analytical -biosensors - environmental 2012

Differential Normal Pulse Voltammetry

Developed for measurement of neurotransmitters

F Gonon et al Analytical Chemistry 56 573-575 (1984)

Voltammetric Analysis

t1

t2 I = I(t2)-I(t1)

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 35: 21   applications analytical -biosensors - environmental 2012

Environmental Analysis

bull Sample matrices

ndashWater

ndashEffluent

ndashSoil

ndashSludge

ndashPlants and derivates

ndashAnimal tissue

ndashAnimal products

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 36: 21   applications analytical -biosensors - environmental 2012

Environmental

bull Heavy Metals

ndashZn Cd Pb Cu Sb Bi Mn Tl

ndashAs Hg Se

ndashNi Co Fe V Mo U Cr

ndashRh Pt

bull Anions

ndashSulphide Sulphite Cyanide

bull Complexing Agents

ndashNTA EDTA

bull Speciation

ndashFree complexed metals

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 37: 21   applications analytical -biosensors - environmental 2012

U (mV)

I (nA

)

-600 -400 -200 0

0

20

40

60

80

100

120

Cd Pb Cu in Tap Water

bull acetate buffer

U (mV)

I (nA

)

-650 -600 -550 -500 -450

0

1

2

U (mV)

I (nA

)

-450 -400 -350 -300 -250

0

25

5

75

10

125

15

Cd 007 ppb

U (mV)

I (nA

)

-250 -200 -150 -100 -50 0 50

25

50

75

100

Pb 17 ppb

Cu 38 ppb

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 38: 21   applications analytical -biosensors - environmental 2012

Ni Co in tap water

Electrolyte ammonia buffer pH 95 + DMG

Ni 034 ppb

Co 021 ppb

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 39: 21   applications analytical -biosensors - environmental 2012

U in tap water

electrolyte 01 mmolL chloranilic acid +

HNO3 pH 18

U (mV)

I (n

A)

20 0 -20 -40 -60 -80 -100 -120

0

-2

-4

-6

-8

-10

-12

-14

U(VI) 1 ppb

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 40: 21   applications analytical -biosensors - environmental 2012

Hg in waste water

ElectrolyteHClO4 + EDTA + NaCl (UV digestion)

Hg 59 microgL

U (mV)

I (micro

A)

350 400 450 500 550 600 650 700

25

3

35

4

45

5

55

6

65

7

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 41: 21   applications analytical -biosensors - environmental 2012

Fe and Mn in tap water

Electrolyte for Mn ammoniaborate buffer

Electrolyte for Fe phosphate buffer + catechol

U (mV)

I (nA

)

-300 -350 -400 -450

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

U (V)

I (nA

)

-155 -15 -145 -14 -135

-10

-20

-30

-40

-50

-60

-70

Mn 21 microgL

Fe 50 microgL

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 42: 21   applications analytical -biosensors - environmental 2012

Rh Pt in tap water

Electrolyte for Rh HCl+ H2COH

Electrolyte for Pt HCl + H2COH + hydrazine

U (V)

I (microA

)

-11 -115 -12

-02

-04

-06

-08

-1

U (V)

I (nA

)

-07 -075 -08 -085 -09 -095

-50

-100

-150

-200

-250

Rh 24 ngL

Pt 35 ngL

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 43: 21   applications analytical -biosensors - environmental 2012

Substance CrDP VR()

U (mV)

I (micro

A)

220 200 180 160 140 120 100 80 60

-06

-07

-08

-09

-1

-11

Cr in tap water

ElectrolyteH2SO4 + diphenylcarbazide UV digestion for oxidation of CrIII to CrVI

Crtotal 47 microgL

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 44: 21   applications analytical -biosensors - environmental 2012

Substance W VR()

U (mV)

I (micro

A)

-325 -300 -275 -250 -225 -200 -175 -150 -125

16

18

2

22

24

26

28

W Ultra Trace Electrode

bull electrolyte H2SO4 + NH4SCN + antipyrine + ascorbic acid + thiourea

WVI 48 microgL

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 45: 21   applications analytical -biosensors - environmental 2012

U (mV)

I (micro

A)

0 -100 -200 -300 -400 -500

-01

-02

-03

-04

-05

-06

-07

-08

-09

-1

-11

NTA EDTA in waste water

Electrolyte HNO3 + ascorbic acid + Bi3+

NTA 23 mgL

EDTA 065 mgL

Bi3+

EDTA

NTA

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 46: 21   applications analytical -biosensors - environmental 2012

Cd and Pb in sea water

Electrolyte HCl + 10 mgL Hg2+ + UV digestion

Cd 182 ngL

Pb 487 ngL

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 47: 21   applications analytical -biosensors - environmental 2012

Ni and Co in sea water

Electrolyte ammonia buffer + DMG

Ni 095 microgL

Co nn

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 48: 21   applications analytical -biosensors - environmental 2012

U in sea water

Electrolyte 01 mmolL chloranilic acid + HNO3 pH 25

U (mV)

I (nA

)

-80 -100 -120 -140 -160 -180 -200

-10

-20

-30

-40

-50

-60

-70

-80

-90

UVI

3 ppm

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 49: 21   applications analytical -biosensors - environmental 2012

Official Methods

bull HMSO Blue Book Method - Metal ions in water ZnCdPbCuVNiCoUAlFe

bull EPA 7472 Hg in aqueous samples by ASV

bull EPA 7063 As in aqueous samples by ASV

bull EPA 97053 Organophosphorous Residues

bull EPA 7198 Cr(VI) in water by polarography

bull DIN 38 406 - ZnCdPbCuNiCo + Tl

bull DIN 38 413 EDTA NTA in Waters

bull ASTM D3557 - 95 Cd in water

bull ASTM D3559 - 96 Pb in water

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 50: 21   applications analytical -biosensors - environmental 2012

CrIII and CrVI in sea water

Electrolyte DTPA + acetate buffer + NaNO2

bull CrVI measuring after reaction time

bull Crtotal direct measurement

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

U (V)

I (n

A)

-11 -12 -13

-20

-40

-60

-80

-100

-120

-140

-160

-180

Crtotal

17 microgL CrVI

047 microgL

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 51: 21   applications analytical -biosensors - environmental 2012

Substance Arsenic VR()

U (mV)

I (micro

A)

-50 0 50 100 150 200

06

08

1

12

14

16

18

AsIII and Astotal in mineral water

AsIII deposition 60 sec at -200 mV

Astotal deposition 120 sec at -1200 mV

Astotal

19 microgL AsIII

064 microgL

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 52: 21   applications analytical -biosensors - environmental 2012

Substance Selenium VR()

U (mV)

I (n

A)

-600 -650 -700 -750

-5

-10

-15

-20

-25

-30

Substance Selenium VR()

U (mV)

I (n

A)

-650 -700 -750

-25

-5

-75

-10

-125

-15

-175

-20

-225

-25

-275

SeIV and Setotal

CSV in (NH4)SO4 + Cu + EDTA pH 22

Setotal UV digestion at pH 7-9

SeIV

16 microgL Setotal

21 microgL

SeIV no sample preparation

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 53: 21   applications analytical -biosensors - environmental 2012

Cyclic Voltammetry

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 54: 21   applications analytical -biosensors - environmental 2012

Cyclic Voltammetry

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 55: 21   applications analytical -biosensors - environmental 2012

Potential applied

Cyclic Voltammetry

1st vertex

2nd vertex one scan

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 56: 21   applications analytical -biosensors - environmental 2012

1st vertex

2nd vertex

59n mV (reversible system)

Ip ~ v12 Current Response Cyclic Voltammetry

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 57: 21   applications analytical -biosensors - environmental 2012

Rapid quantitative technique

bullReversible or irreversible (Ep as a function of v)

bullNumber of electrons (Peak separation 59n mV)

bullDiffusion coefficient

bullFaradaic (I~v12) vs Capacitive current (I~v)

Cyclic Voltammetry

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 58: 21   applications analytical -biosensors - environmental 2012

Potential and Current step methods

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 59: 21   applications analytical -biosensors - environmental 2012

bull Chrono-amperometry - Kinetic measurements - Electrolysis

bull Chrono-potentiometry

- Battery chargingdischarging - Coulometric titration - Measuring change in OCP (corrosion potential) over time

Potential and Current step methods

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 60: 21   applications analytical -biosensors - environmental 2012

Multi Mode Electrochemical Detection

CE

RE WE

Flow cell

IC Or HPLC Pump

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 61: 21   applications analytical -biosensors - environmental 2012

WE = GCE Glassy Carbon Electrode UTGE Ultra Trace Graphite Electrode Carbon Paste Electrode Metal Electrodes (Pt Ag Au) Amalgamated ldquohome maderdquo Electrodes CE = Au RE= AgAgCl ELECTRODE

Multi Mode Electrochemical Detection

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 62: 21   applications analytical -biosensors - environmental 2012

DC AMPEROMETRY One potential level MULTIPULSE AMPEROMETRY Up to 10 potential levels DIFFERENCIAL PULSE AMPEROMETRY Up to 10 potential levels with the possibility to choose which level subtract

Multi Mode Electrochemical Detection

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 63: 21   applications analytical -biosensors - environmental 2012

01 mM (20 ul) AA NA DOPAC 5-HIAA

ChromSpher C18 part size 5um

0 500 1000 1500 2000 2500 3000 35000

-60100x10

-60200x10

-60300x10

-60400x10

-60500x10

-60600x10

-60700x10

-60800x10

t s

i A

9 Potential levels

HPLC column

Determination of AA (ascorbic Acid) NA DOPAC (34-dihydroxyphenylacetic acid) 5-HIAA (5-hydroxyindoleacetic acid)

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 64: 21   applications analytical -biosensors - environmental 2012

bull AROMATIC HYDROXY COMPOUNDS - antioxidants flavones phenols tocopherols bull AROMATIC AMINES - anilines benzidines bull INDOLS bull PHENOLTHIAZINE bull MERCAPTANES bull VITAMIN A VITAMIN C VITAMIN K1 bull NITRO COMPOUNDS - nitrophenols nitroglicerin bull INORGANICS ANIONS - NO2

- SO3-2 S2O3

-2 ClO2- SCN- CN-

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 65: 21   applications analytical -biosensors - environmental 2012

Thin layer Flow Cell

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 66: 21   applications analytical -biosensors - environmental 2012

Amperometric with Flow Injection Analysis

Time (s)

400 600 800

Cu

rren

t (A

)

Pump

Injector EC Detector

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 67: 21   applications analytical -biosensors - environmental 2012

Environmental applications

Heavy metals Organics elements

Determination

bull Differential pulse voltammetry bull Square wave voltammetry bull Chrono amperometry bull Potentiometric stripping analysis bull Flow injection multimode electrochemical detections

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 68: 21   applications analytical -biosensors - environmental 2012

Environmental applications

Heavy metals Organics elements

Determination

bull Mercury Electrode (DP SQW) bull Solid state electrode GC Pt Au (DP SQW PSA)

bull Biosensors Chrono Amperometry Flow injection DP amperometry bull Imunosensors same as biosensors

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 69: 21   applications analytical -biosensors - environmental 2012

What is Biosensor

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 70: 21   applications analytical -biosensors - environmental 2012

BIOSENSOR

SAMPLE

Aquisition

ELABORATION

BIORECEPTOR

- Enzymes - Microorganisms - Antibodies - Plant animal tissues

TRANSDUCER

- Electrodes - FET - Thermistors - Optical fibers - Piezoelectric

SIGNAL

What is Biosensor A self-contained integrated device which is capable of providing specific quantitative or semi-quantitative analytical information using a biological recognition element which is in direct spatial contact with a transducer element

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 71: 21   applications analytical -biosensors - environmental 2012

Mechanism of a Biosensors

Tra

nsducer

Recepto

r

Measurable Signal

=Analyte

Solution

NO Measurable

Signal

RECOGNITION NO RECOGNITION

Thin selective membrane

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 72: 21   applications analytical -biosensors - environmental 2012

- Uses of Biosensors - bull Quality assurance in agriculture food and pharma industries ex determination of EColi Salmonella bull Monitoring environmental pollutants amp biological warfare agents ex determination pesticides anthrax spores Heavy metals bull Medical diagnostic ex Glucose determination PSA Troponin T bull Biological assays ex DNA microarrays

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 73: 21   applications analytical -biosensors - environmental 2012

- Classes of Biosensors -

A)Catalytic biosensors

Kinetics devices that measure steady-state concentration of a transducer-detectable species formed or lost due to a biocatalytic reaction

bull Monitored quantities

rate of product formation Disappearance of a reactant Inhibition of a reaction

bull Biocatalysts used

bull Enzymes Microorganisms Organelles Tissue samples

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 74: 21   applications analytical -biosensors - environmental 2012

- Classes of Biosensors -

B)Affinity biosensors

Devices in which receptor molecules bind analyte molecules ldquoirreversiblyrdquo causing a physicochemical change that is detected

bull Receptor molecules

Antibodies Nucleic acids Hormone receptors

Biosensors today are most often used to detect molecules of biological origin based

on specific interactions

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 75: 21   applications analytical -biosensors - environmental 2012

O - ring

Polycarbonate Membrane

Biocatalytic Membrane

Permeable Membrane

biosensors components

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 76: 21   applications analytical -biosensors - environmental 2012

1) To the amplifier

2) Body of the sensor

3) AgAgCl Electrode

4) Pt Electrode

5) Removing cap

6) O2 or H2O2 permeable membrane

amperometric sensor

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 77: 21   applications analytical -biosensors - environmental 2012

- Detection Elements -

Catalysis strategies enzimes most common

Glucose oxidase urease alcohol oxidase etc Commercial example glucose sensor using glucose oxidase (GOD)

Commercially available Biosensors Glucose lactate alcohol sucrose galactose uric acid alpha amylase choline L-Lysine (all amperometric based)

Glucose + O2 + H2O Gluconic acid + H2O2

Measurements routes - pH Change (acid production) - O2 Consumption (fluorophore monitor) - H202 production (electrochemical)

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 78: 21   applications analytical -biosensors - environmental 2012

Oxygen Electrode

Anode AgAgCl (reference electrode)

Cathode Pt (working electrode)

E= -700 mV

Hydrogen peroxide sensor

Cathode AgAgCl (reference electrode)

Anode Pt (working electrode)

E= +700 mV

- Detection Elements -

H2O2 O2+ 2 H+ + 2e-

12O2+ 2 H+ + 2e- H2O

O2 + 4H+ + 4e- 2 H2O Ag Ag+ + 1e-

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 79: 21   applications analytical -biosensors - environmental 2012

- Detection Elements -

1st Generation Biosensors base on direct determination of one of the reaction product or consume of Oxigen

S P

O2 H2O2

e-

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 80: 21   applications analytical -biosensors - environmental 2012

Sugar catalysis by oxidoreductases

FADH2

FAD

O CH2OH

HO

HO OH O

OH

O CH2OH

HO

HO OH

H Glucose

Gluconolactone

2H+ + 2e-

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 81: 21   applications analytical -biosensors - environmental 2012

- Detection Elements -

2nd Generation Biosensors involve specific mediators between the reaction and the transducer in order to generate improved response

S P

Mox Mred

e-

Substrate

product

Ele

ctro

de

Important points for the mediator Low redox potential reversible molecule fast kinetic electron transfer high stability

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 82: 21   applications analytical -biosensors - environmental 2012

CV catalytic reaction oxidase enzyme mediate with carboxylferrocene (05mM)

a)No substrate b)Substrate 25 mM c)Substrate 5 mM scanrate 5 mVs

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 83: 21   applications analytical -biosensors - environmental 2012

- Detection Elements -

3rd Generation Biosensors the reaction itself causes the response and no product or mediator diffusion is directly involved

S P

e-

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 84: 21   applications analytical -biosensors - environmental 2012

- Transducers -

Electrochemical translate a chemical event to an electrical event by measuring current passed (amperometric detection is the most common) potential change between the electrodes etc

Response measurements with cellobiose biosensor

GC electrode

0 100 200 300 400 500 600 700 8000

-5010x10

-5020x10

t s

i A

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 85: 21   applications analytical -biosensors - environmental 2012

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 86: 21   applications analytical -biosensors - environmental 2012

- Transducers -

Piezoelectric translate a mass change from a chemical adsorption event to electrical signal

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 87: 21   applications analytical -biosensors - environmental 2012

Ideal Biosensors characteristics

bull Sensitivity high ΔSignal Δconcentration analyte

bull Simple calibration (with standards)

bull Linear response ΔSignal Δconc Constant over large concentration range

bull Background signal low noise

bull No hysteresis signal independent of prior history of measurements

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 88: 21   applications analytical -biosensors - environmental 2012

Ideal Biosensors characteristics

bull Selectivity response only to changes in target analyte concentration

bull Long term stability not subject of fouling poisoning oxide formation that interferes with the signal

bull Dynamic response rapid response to variation in analyte concentration

bull Biocompatibility minimize clotting platelet interactions activation of complement

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 89: 21   applications analytical -biosensors - environmental 2012

WHY ELECTROCHEMICAL BIOSENSORS

ELECTROCHEMICAL BIOSENSORS

High selectivity

Disposable reusable sensor Small amount of

sample

Sensitivity accuracy and reproducibility

Fast response

time

Screening and monitoring of real matrices

Miniaturization

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 90: 21   applications analytical -biosensors - environmental 2012

Future directions on applications

bull Multi analyte capability (proteins biowarfare agents pathogens etc)

bull Integration ndash miniaturization (microfluidic ldquolab on a chiprdquo devices)

bull Implantable devices (ex Medtronic glucose sensor implant in major vein of the heart)

bull Living cells ndash tissue as biological element

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 91: 21   applications analytical -biosensors - environmental 2012

Future directions on basic research

bull Development of tools for basic research and investigation of new biosensors Spectroelectrochemistry surface modification (FRA) ESPR EQCM

bull Production of more redox enzymes

bull Site directed mutagenesis

bull Development of applications with already existing biosensors

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 92: 21   applications analytical -biosensors - environmental 2012

Some examples

bull Biosensors for Heavy Metals

bull Modify screen print electrodes

bull Sensors for organics elements

bull Sensors in food applications

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 93: 21   applications analytical -biosensors - environmental 2012

Disposable electrochemical sensor for rapid determination of heavy metals in herbal drugs

bull I Palchettia M Mascini a M Minunnia A R Biliab and F F Vincierib

bull a Dipartimento di Chimica Universitagrave degli Studi di Firenze ndash Polo Scientifico Via della Lastruccia 3 50019 Firenze Italy

bull b Dipartimento di Scienze Farmaceutiche Via G Capponi 9 50100 Firenze Italy

bull Abstract

bull Analysis of herbal drugs and extracts need rapid and affordable methods to assure the quality of products The application of the electrochemical sensors in the field of quality control of herbal drugs herbal drug preparations and herbal medicinal products appears very promising advantageous and alternative to conventional methods due to their inherent specificity simplicity and for the fast response obtained This paper presents a proposal about the application of disposable electrochemical sensors associated with electroanalytical instrumentation for the detection of heavy metal analysis in herbal drugs In particular samples of St Johns wort were analysed applying anodic stripping voltammetry The content of Cd and Pb were evaluated

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 94: 21   applications analytical -biosensors - environmental 2012

Ca10(PO4)6(OH)2-modified carbon-paste electrode for the determination of trace lead(II) by square-wave voltammetry

bull MA El Mhammedia M Achakb and A Chtainia

bull aEquipe drsquoElectrochimie et des Mateacuteriaux Inorganiques Universiteacute Cadi Ayyad Faculteacute des Sciences et Techniques BP 523 23000 de Beni-Mellal Morocco

bull bLaboratoire drsquoHydrobiologie et drsquoAlgologie Faculteacute des Sciences Semlalia Universiteacute Cadi Ayyad Marrakech Morocco

bull Abstract

bull The analytical performance of hydroxyapatite Ca10(PO4)6(OH)2(HAp) screen-printed sensors designed for the detection of metals was evaluated The suitable HAp-modified carbon-paste electrode (HAp-CPE) for the electrochemical determination of lead is illustrated in this work using cyclic and square-wave voltammetry in the potential range between minus03 and minus08 V The voltammetric measurements were carried out using as working electrode HAp-CPE and a platinum electrode and an SCE electrode as auxiliary and reference electrodes respectively Under the optimized working conditions calibration graph is linear for 5 min of preconcentration time with the detection limit 768 times 10minus10 mol Lminus1

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 95: 21   applications analytical -biosensors - environmental 2012

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

bull EO Jorgea MMM Netoa b and MM Rochaa bull aDepartamento de Quiacutemica e Bioquiacutemica Centro de Ciecircncias Moleculares e

Materiais Faculdade de Ciecircncias Universidade de Lisboa Campo Grande Ed C8 1749-016 Lisboa Portugal

bull bDepartamento de Quiacutemica Agriacutecola e Ambiental Instituto Superior de Agronomia TULisbon Tapada da Ajuda 1349-017 Lisboa Portugal

bull Abstract bull A bismuth film electrode was tested and proposed as an environmentally

friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ using acetate buffer as the supporting electrolyte The stripping step was carried out by a square wave potential-time excitation signal Under the selected optimised conditions a linear calibration plot was obtained in the submicromolar concentration range allowing the electrochemical determination of thallium in trace amounts the calculated detection limit was 108 nM and the relative standard deviation for 15 measurements of 01 μM Tl(I) was plusmn02 for a 120 s accumulation time Interference of other metals on the response of Tl(I) was investigated Application to real environmental samples was tested

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 96: 21   applications analytical -biosensors - environmental 2012

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

bull Wilney JR Santosa Phabyanno R Limaa Auro A Tanakab Socircnia MCN Tanakab and Lauro T Kubotaa

bull aDepartment of Analytical Chemistry Institute of Chemistry University of Campinas ndash UNICAMP 13084-971 Campinas SP Brazil

bull bDepartment of Chemistry Technology Center Technological University Federal of Maranhatildeo ndash UFMA 65085-040 Satildeo Luiacutes MA Brazil

bull Abstract bull A glassy carbon (GC) electrode modified with alternated layers of iron(III)

tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV) This modified electrode showed excellent catalytic activity for the nitrite oxidation After optimizing the operational conditions a linear response range from 05 to 75 μmol lminus1 with a low detection limit of 01 μmol lminus1 was obtained The proposed sensor was stable with a sensitivity of 200 μA 1 μmolminus1 and good repeatability evaluated in terms of relative standard deviation (RSD = 13) for n = 10 Possible interferences from several common ions were evaluated This sensor was applied for the voltammetric determination of nitrite in some food samples

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 97: 21   applications analytical -biosensors - environmental 2012

Cadmium zinc and copper biosorption mediated by Pseudomonas veronii 2E

Diana L Vullo a Helena M Cerettia Mariacutea Alejandra Daniela Silvana AM Ramiacutereza and Anita Zaltsa

bull aAacuterea Quiacutemica Instituto de Ciencias Universidad Nacional de General Sarmiento JM Gutieacuterrez 1150 (B1613GSX) Los Polvorines Buenos Aires Argentina

bull Abstract

bull Adsorption properties of bacterial biomass were tested for Cd removal from liquid effluents Experimental conditions (pH time cellular mass volume metal concentration) were studied to develop an efficient biosorption process with free or immobilised cells of Pseudomonas veronii 2E Surface fixation was chosen to immobilise cells on inert surfaces including teflon membranes silicone rubber and polyurethane foam Biosorption experiments were carried out at 32 degC and controlled pH maximal Cd(II) retention was observed at pH 75 The isotherm followed the Langmuir model (Kd = 017 mM and qmax = 048 mmolg cell dry weight) Small changes in the surface negative charge of cells were observed by electrophoretic mobility experiments in presence of Cd(II) In addition biosorption of 40 Cu(II) (pH 5 and 62) and 50 Zn(II) and 50 Cd(II) (pH 75) was observed from mixtures of Cu(II) Zn(II) and Cd(II) 05 mM each

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 98: 21   applications analytical -biosensors - environmental 2012

Detection of pesticide by polymeric enzyme electrodes

K Duttaa D Bhattacharyaya A Mukherjeeb SJ Setfordc APF Turnerc and P Sarkara

bull aDepartment of Polymer Science and Technology University of Calcutta 92 APC Road Kolkata 700009 India

bull bDepartment of Chemical Engineering Jadavpur University Kolkata 700032 India

bull cCranfield Health Cranfield University Silsoe BEDS MK45 4DT UK bull Abstract bull Screen-printed electrodes (SPEs) containing immobilized

acetylcholine esterase (AChE) enzyme were used for the electrochemical determination of organophosphorous (OP) and carbamate pesticides The extent of AChE deactivation by the pesticide was determined in the presence of acetylcholine (AChCl) substrate The unique nature of this approach lies in the enzyme immobilization procedure in which AChE was attached to the SPE by in situ bulk polymerization of acrylamide to ensure efficient adherence within the membrane with minimal losses in enzyme activity Responses were observed for the pesticides Monocrotophos Malathion Metasystox and Lannate over the concentration range 0ndash10 ppb (μg Lminus1)

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 99: 21   applications analytical -biosensors - environmental 2012

Determination of selenium in Italian rices by differential pulse cathodic stripping voltammetry Monica Panigatia Luigi Falciolab Patrizia Mussinib

Giangiacomo Berettac and Roberto Maffei Facinoc bull aDepartment of Inorganic Metallorganic and Analytical Chemistry Faculty

of Pharmacy University of Milano Via Venezian 21 20133 Milano Italy bull bDepartment of Physical Chemistry and Electrochemistry Faculty of

Science University of Milano Via Golgi 19 20133 Milano Italy bull cInstitute of Pharmaceutical and Toxicological Chemical Faculty of

Pharmacy University of Milano Viale Abruzzi 42 20131 Milano Italy bull Abstract bull The total selenium content in white black red rice and white rice hull

samples grown in Northern Italy cultivars has been determined using the differential pulse cathodic stripping voltammetry (DPCSV) on the hanging drop mercury electrode (HDME) in the presence of Cu(II) The digestion was performed in open vessel through a combination of wet aciddry ashing with Mg(II) salts The calibration curve was linear in the concentration range 015ndash8 ppb the detection limit was estimated to be 007 ppb and the recovery was in the range 85ndash102 Reproducibility was from 19 to 90 (RSD n = 4) The resulting selenium contents in different Italian rice varieties were 201 plusmn 18 ppb (white) 30 plusmn 10 ppb (red) 267 plusmn 13 ppb (black) 453 plusmn 41 ppb (white rice hull)

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 100: 21   applications analytical -biosensors - environmental 2012

Determination of fenthion and fenthion-sulfoxide in olive oil and in river water by square-wave adsorptive-stripping voltammetry T Galeano Diacuteaz a A Guiberteau Cabanillasa MD Loacutepez Sotoa

and JM Ortiza

bull aDepartment of Analytical Chemistry University of Extremadura Avd Elvas sn 06071 Badajoz Spain

bull Abstract

Square-wave adsorptive-stripping voltammetry technique has been used to develop a method for the determination of fenthion in olive oil Fenthion is isolated from olive oil by carrying out a solidndashliquid extraction procedure using silica cartridge followed by a liquidndashliquid partitioning with acetonitrile The detection limit in olive oil is 788 ng gminus1 On the other hand it has been developed a method for the simultaneous determination of fenthion and its metabolite fenthion-sulfoxide in river water The detection limits are 041 ng gminus1 and 044 ng gminus1 for fenthion and fenthion-sulfoxide respectively Recoveries for three levels of fortification are ranged from 96 to 103 for fenthion and 94 to 104 for fenthion-sulfoxide

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 101: 21   applications analytical -biosensors - environmental 2012

Development of urease and glutamic dehydrogenase amperometric assay for heavy metals screening in polluted samples Belen Bello Rodriguez John A Bolbot and Ibtisam E

Tothill

bull Cranfield Biotechnology Centre Institute of Bioscience Cranfield University Silsoe Bedforshire MK45 4DT UKAbstract

bull The enzyme urease catalyses the hydrolysis of urea and the formation of NH4+ is determined using a NADH-glutamate dehydrogenase coupled reaction system NADH consumption is monitored amperometrically using screen-printed three electrode configuration and its oxidation current is then correlated to urease activity The linear range obtained for Hg(II) and Cu(II) was 10ndash100 μg lminus1 with a detection limit of 72 μg lminus1 and 85 μg lminus1 respectively Cd(II) and Zn(II) produced enzyme inhibition in the range 1ndash30 mg lminus1 with limits of detection of 03 mg lminus1 for Cd(II) and 02 mg lminus1 for Zn(II)

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 102: 21   applications analytical -biosensors - environmental 2012

Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology

bull Emma Muntildeoz and Susana Palmero

bull Departamento de Quiacutemica (Aacuterea de Quiacutemica Analiacutetica) Facultad de Ciencias Universidad de Burgos PMisael Bantildeuelos sn 09001 Burgos Spain

bull Abstract

bull A methodology for the determination of Zn(II) Cd(II) and Pb(II) directly in dissolved honey samples by potentiometric stripping analysis with a flow cell is proposed Heavy metals in honey are of interest not only for quality control but can be used also as an environmental indicator In this work honey samples were collected in different places of Burgos (Spain) Lead (II) and cadmium (II) can be directly determined The results were compared with inductively coupled mass plasma spectrometry as reference method

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 103: 21   applications analytical -biosensors - environmental 2012

Screen print electrodes

Carbon SPE

Gold SPE

Platinum SPE

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 104: 21   applications analytical -biosensors - environmental 2012

Screen print electrodes

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 105: 21   applications analytical -biosensors - environmental 2012

Disk electrodes in any material Al Ag Au Cu Fe Hf Nb Ni Pb Pd Pt Ta Ti Sn Zn Zr Y

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 106: 21   applications analytical -biosensors - environmental 2012

Preparation of electronic tongue EQCM

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 107: 21   applications analytical -biosensors - environmental 2012

- EQCM -

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 108: 21   applications analytical -biosensors - environmental 2012

EQCM application ndash Metal UPD

bull UPD stands for Under-Potential Deposition

ndashUPD leads to the electrolytic formation a metal layer at potentials gt E

bull Interaction between substrate and metal ions

ndashDeposition mode leads to a single monolayer of metal

ndash Ideal system for EQCM validation

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 109: 21   applications analytical -biosensors - environmental 2012

2

2

255987Hzm 314094ng cm

00815Hz ng cm

f(Hz) 255987Hz

EQCM application ndash Pb UPD Au

bull Data analysis

ndash Average f for the formation of Pb UPD on

Au

ff m C

2

fC 00815Hz ng cm

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 110: 21   applications analytical -biosensors - environmental 2012

2

QCMm 314094ng cm

2PbPb Pb

Qm M 32454 ng cm

2F

bull Data analysis

ndashRequired charge for Pb UPD on Au

2

PbQ 302 C cm

EQCM application ndash Pb UPD Au

Good agreement

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 111: 21   applications analytical -biosensors - environmental 2012

EIS multianalyte sensing with an automated SIA system An electronic tongue employing the impedimetric signal

Montserrat Cortina-Puiga Xavier Muntildeoz-Berbelb M Asuncioacuten Alonso-Lomillob Francisco J Muntildeoz-Pascualb and Manuel del Vallea

bull aSensors and Biosensors Group Department of Chemistry Autonomous University of Barcelona Edifici Cn Barcelona E-08193 Spain

bull bNational Centre of Microelectronics (IMB-CNM) CSIC Campus of Autonomous University of Barcelona Barcelona E-08193 Spain

bull Abstract bull In this work the simultaneous quantification of three alkaline ions

(potassium sodium and ammonium) from a single impedance spectrum is presented For this purpose a generic ionophore ndash dibenzo-18-crown-6 ndash was used as a recognition element entrapped into a polymeric matrix of polypyrrole generated by electropolymerization Electrochemical impedance spectroscopy (EIS) and artificial neural networks (ANNs) were employed to obtain and process the data respectively A sequential injection analysis (SIA) system was employed for operation and to automatically generate the information required for the training of the ANN Three commercial fertilizers were tested employing the proposed methodology on account of the high complexity of their matrix The experimental results were compared with reference methods

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 112: 21   applications analytical -biosensors - environmental 2012

Amperometric sensors based on poly(34-ethylenedioxythiophene)-modified electrodes Discrimination of white wines L Pigania G Focab K Ionescua V Martinaa A Ulricib F Terzia M

Vignalic C Zanardia and R Seebera bull bDipartimento di Scienze Agrarie e degli Alimenti Universitagrave degli Studi di

Modena e Reggio Emilia Padiglione Besta via Amendola 2 42100 Reggio Emilia Italy

bull aDipartimento di Chimica Universitagrave di Modena e Reggio Emilia via GCampi 183 41100 Modena Italy

bull cVinicola San Nazaro Via Gonzaga 12 46020 Pegognaga (MN) Italy bull Abstract bull The voltammetric responses on selected white wines of different vintages and

origins have been systematically collected by three different modified electrodes in order to check their effectiveness in performing blind analysis of similar matrices The electrode modifiers consist of a conducting polymer namely poly(34-ethylenedioxythiophene) (PEDOT) and of composite materials of Au and Pt nanoparticles embedded in a PEDOT layer Wine samples have been tested without any prior treatments with differential pulse voltammetry technique The subsequent chemometric analysis has been carried out both separately on the signals of each sensor and on the signals of two or even three sensors as a unique set of data in order to check the possible complementarity of the information brought by the different electrodes After a preliminary inspection by principal component analysis classification models have been built and validated by partial least squares-discriminant analysis

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 113: 21   applications analytical -biosensors - environmental 2012

Electrochemical elimination of contaminants

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 114: 21   applications analytical -biosensors - environmental 2012

Electrochemical dissolution of contaminants

High Potential High current applications Autolab Booster 20A

Foto do sistema utilizado para tratamento de chorume e representaccedilatildeo esquemaacutetica do reator eletroquiacutemico

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 115: 21   applications analytical -biosensors - environmental 2012

Kinetics of the oxidation of formaldehyde in a flow electrochemical reactor with TiO2RuO2 anode

Mara Terumi Fukunagaa Joseacute Roberto Guimaratildeesa and Rodnei Bertazzolib

bull aDepartamento de Saneamento e Ambiente Faculdade de Engenharia Civil Arquitetura e Urbanismo Universidade Estadual de Campinas CP 6021 13083-852 Campinas SP Brazil

bull bDepartamento de Engenharia de Materiais Faculdade de Engenharia Mecacircnica Universidade Estadual de Campinas CP 6122 13083-970 Campinas SP Brazil

bull Abstract

bull This paper reports the electrochemical degradation of solutions containing formaldehyde by means of an electrochemical tubular flow reactor with a titanium anode coated with metal oxides (TiRu03Ti07O2) Due to the simplicity and low molecular weight of the compound it was possible to achieve high mineralization rates the oxidation reaction of formaldehyde as well as TOC and COD removal were controlled by mass transfer For solutions with 04 g Lminus1 of formaldehyde electrodegradation followed a pseudo first-order kinetics and the mass transport coefficients were calculated After the experiments a 97 reduction of TOC was observed and the final formaldehyde and COD concentrations were below the detection limit threshold

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 116: 21   applications analytical -biosensors - environmental 2012

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide Study for the degradation of 24-dichlorophenoxyacetic acid Carla Badellinoa Christiane Arruda Rodriguesa and Rodnei

Bertazzoli a

bull aFaculty of Mechanical Engineering Department of Materials Engineering State University of Campinas CP 6122 13083-970 Campinas Sao Paulo Brazil

bull Abstract

bull This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode and the optimization of the O2 reduction rate relative to cell potential A study for the simultaneous oxidation of the herbicide 24-dichlorophenoxyacetic acid (24-D) by the in situ electrogenerated H2O2 is also reported First order apparent rate constants for 24-D degradation ranged from 09 to 63 times 10minus5 m sminus1 depending on the catalyst used (UV or UV + Fe(II)) TOC reduction was favored in acidic medium where a decreasing of 69 of the initial concentration was observed in the process catalyzed by UV + Fe(II)

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

tra

zin

a]

m

g L

-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 117: 21   applications analytical -biosensors - environmental 2012

Electrochemical dissolution of contaminants

00 05 10 15 20

0

5

10

15

20

0033 M Na2SO

4

010 M NaCl

010 M NaNO3

010 M NaOH

010 M NaClO4

0033 M H2SO

4[a

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zin

a]

m

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-1

t h

Electrolysis and Atrazina concentration

(i = 40 mA cm-2)

Artur de Jesus Motheo Dep de Fiacutesico-Quiacutemica Instituto de Quiacutemica de Satildeo Carlos USP BR

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 118: 21   applications analytical -biosensors - environmental 2012

Electrochemical deposition of silver and gold from cyanide leaching solutions

bull Reyes-Cruz Victor Ponce de Leon Carlos Gonzaacutelez Ignacio and Oropeza MercedesT (2002) Electrochemical deposition of silver and gold from cyanide leaching solutions Hydrometallurgy 65 (2-3) 187-203

bull Abstract

bull A systematic voltammetric study developed in this work allows the determination of the potential range at which the selective deposition of gold and silver is carried out in the presence of a high content of copper Also the voltammetric study of a cyanide solution containing low concentrations of Au(I) and Ag(I) free of and with high concentration of Cu(I) was carried out The study shows the potential range at which Au(I) and Ag(I) are reduced despite the high concentration of the Cu(I) ions The deposition of gold and silver was not interfered with by the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-LC with a reticulated vitreous carbon (RVC) cathode

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants

Page 119: 21   applications analytical -biosensors - environmental 2012

Electrochemical environmental applications

Determination of Heavy metals

Determination of organics pollution elements

Preparations of Sensors biosensors imunosensors

Preparation of electronic tongue EQCM

Electrochemical dissolution of contaminants