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Transcript of 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
22
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.
44
Bacterial Fuel CellsBacterial Fuel Cells
A microbial fuel cell converts chemical energy, available in a bio-convertible substrate, directly into electricity.
55
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
66
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
77
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
88
Catalytic Electron Transfer Mechanisms from T-cellsCatalytic Electron Transfer Mechanisms from T-cellsE
LE
CT
RO
DE
EL
EC
TR
OD
E
HH22QQ
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
99
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
1111
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
1212
Scanning Electrochemical MicroscopyScanning Electrochemical Microscopy
1313
Patch ClampPatch ClampIon Transfer through Cellular MembranesIon Transfer through Cellular Membranes
1414
Protein-Film VoltammetryProtein-Film Voltammetry
1515
Protein-Film and Cyclic VoltammetryProtein-Film and Cyclic Voltammetry
1616
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--
1919
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
55
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
40
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
2424
Q10 chemical transformation in a basic mediumQ10 chemical transformation in a basic medium
2525
Caclium complexation with Q10-hydroxylated Caclium complexation with Q10-hydroxylated derivativesderivatives
2626
Caclium complexation with Q10-hydroxylated Caclium complexation with Q10-hydroxylated derivativesderivatives