1 bioelectrochemistry: from biofuel cells to membrane electrochemistry valentin mirčeski institute...

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Bioelectrochemistry: From Biofuel Bioelectrochemistry: From Biofuel Cells to Membrane ElectrochemistryCells to Membrane Electrochemistry

Valentin MirValentin MirččeskieskiInstitute of Chemistry

Faculty of Natural Sciences and Mathematics

“Ss. Cyril and Methodius” University, Skopje

Republic of Macedonia

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Electricity production using living microorganisms

Studying the interrelation between the chemical and electrical

phenomena in living organisms

Major Goals:Major Goals:

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Galvanic CellGalvanic Cell

A Galvanic cell converts chemical energy into electricity.

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Bacterial Fuel CellsBacterial Fuel Cells

A microbial fuel cell converts chemical energy, available in a bio-convertible substrate, directly into electricity.

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Finneran, K.T., Johnsen, C.V. & Lovley, D.R. Int. J. Syst. Evol. Microbiol. 53, 669–673 (2003).

Disadvantages

Power outputs - miliwats. Yet no commercially applications

80% electron efficiency

Advantages

Electricity generation out of wastewater Glucose-poweredpacemakersBio-sensors, and nutrient removal systems

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paraffin-impregnated graphite electrode

T-cells

-5.E-06

0.E+00

5.E-06

-0.6 -0.2 0.2 0.6 1

E vs Ag/AgCl (3 M KCl) / V

I/A

Lymphocytes Immobilized on a Graphite ElectrodeLymphocytes Immobilized on a Graphite Electrode

reference electrode counter electrode

Fluorescent image of cells attached to the electrode.

Cyclic Voltammetry

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reference electrode

Electron Transport Catalyzed by a Redox MediatorElectron Transport Catalyzed by a Redox Mediator

paraffin-impregnated graphite electrode

adsorbed redox mediator

counter electrode

Redox Mediator2-palmytoilhydroquinone

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Catalytic Electron Transfer Mechanisms from T-cellsCatalytic Electron Transfer Mechanisms from T-cellsE

LE

CT

RO

DE

EL

EC

TR

OD

E

HH22QQ

QQ

T-cellsT-cells(reduced form)(reduced form)

2e2e--

H2Q/Q - a redox catalyst

T-cellsT-cells(oxidized form)(oxidized form)

-4

-3

-2

-1

0

1

2

3

4

-0.7 -0.2 0.3 0.8 1.3 E vs Ag/AgCl (3 M KCl) / V

I /

H2Q

H2Q + T-cells

V. Mirceski et al. in press: Clinical Chemistry and Laboratory Medicine 

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Electrochemistry at a Single CellElectrochemistry at a Single CellUltramicroelectrodesUltramicroelectrodes

Image of a disk ultramicroelectrode by electronic microscopy

Typical dimensions within the interval:

10-6 to 10-9 m

1010

Cartoon of a neuronal chemical synapse

Exocytose of NeurotransmittersExocytose of Neurotransmitters

Exocytose

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Amperometric Detection of Exocytotic EventsAmperometric Detection of Exocytotic Events

Series of single vesicular exocytotic events observed through amperometric oxidation of adrenaline molecules

From: C Amatore et al. ChemPhysChem 2003, 4, 147-154

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Scanning Electrochemical MicroscopyScanning Electrochemical Microscopy

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Patch ClampPatch ClampIon Transfer through Cellular MembranesIon Transfer through Cellular Membranes

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Protein-Film VoltammetryProtein-Film Voltammetry

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Protein-Film and Cyclic VoltammetryProtein-Film and Cyclic Voltammetry

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The electrode takes the place of one of the enzyme's physiological redox partners.

Controlling the electrode potential one controls the rate of the electron exchange

Controlling the rate of change of the electrode potential, one precisely controls the enzyme's access to substrate

Catalysis with Redox Active EnzymesCatalysis with Redox Active Enzymes

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Coupling of the Redox Chemistry with Ion Transfer at Cellular Coupling of the Redox Chemistry with Ion Transfer at Cellular MembranesMembranes

K+ channel complex that catalyzes a redoxreaction.

K+

S. H. Heinemann et al. Science STCE, 2006, 350, 33.

K+

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Voltammetry of Artificial MembranesVoltammetry of Artificial MembranesCoupled Electron-Ion Transfer ReactionCoupled Electron-Ion Transfer Reaction

Edge Plane Pyrolytic Graphite Electrode

Red Ox+XX--

Organic film

Aqueous electrolyteCat+X-

Reference electrode

- e-

XX--

Organic electrolyteTBA+X-

Counter Electrode

RedRed(o)(o) + X + X--(aq)(aq) ⇄⇄ Ox Ox++

(o)(o) + X + X--(o)(o) + e + e--

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SO42-

CH3COO-Br-

NO3-

SCN-

ClO4-

0 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800

10

15

20

25

30

35

40

45

50

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E vs SCE / V

I / A

Role of the Transferring IonsRole of the Transferring Ionson the Redox Chemistry of the Membraneon the Redox Chemistry of the Membrane

SW voltammograms for the oxidation of a lutetium complex in the nitrobenzene SW voltammograms for the oxidation of a lutetium complex in the nitrobenzene membranemembrane

2020

Red Ox+X-

-e

X-

Edge Pyrolytic Graphite Electrode

Cholesterol Membrane at the Liquid|Cholesterol Membrane at the Liquid|Liquid Liquid InterfaceInterface

2121

-0.350 -0.250 -0.150 -0.050 0 0.050-7.5

-5.0

-2.5

0

2.5

5.0

7.5

E vs. SCE / V

I / A

1

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ClOClO44--

Monitoring of the Cholesterol Membrane Formation Monitoring of the Cholesterol Membrane Formation with Cyclic Voltammetrywith Cyclic Voltammetry

2222

E / V-0.400 -0.200 0 0.100 0.300 0.400

-10

-7.5

-2.5

0

2.5

7.5

10I /

A

with cholesterol

no cholesterol

NONO33--

Cholesterol Facilitates the Transfer kinetics of ClOCholesterol Facilitates the Transfer kinetics of ClO44--, NO, NO33

-- and SCNand SCN--

2323

Q10 electrochemistryQ10 electrochemistry

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Q10 chemical transformation in a basic mediumQ10 chemical transformation in a basic medium

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Caclium complexation with Q10-hydroxylated Caclium complexation with Q10-hydroxylated derivativesderivatives

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Caclium complexation with Q10-hydroxylated Caclium complexation with Q10-hydroxylated derivativesderivatives