21 applications analytical -biosensors - environmental 2012
TRANSCRIPT
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
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
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
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
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
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
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
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
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
- 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
- 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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
- 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
- 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
- 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
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
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
- 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
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
- 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
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
- 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
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
- 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
- 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
- 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
- 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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
- 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
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
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
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
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
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
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
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
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
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
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
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
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