Bioelectrochemistry: From Biofuel Cells to Membrane Electrochemistry

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Bioelectrochemistry From Biofuel Cells to
Membrane Electrochemistry

• Valentin Mirceski
• Institute of Chemistry
• Faculty of Natural Sciences and Mathematics
• Ss. Cyril and Methodius University, Skopje
• Republic of Macedonia

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Major Goals

• Electricity production using living
  microorganisms
• Studying the interrelation between the
  chemical and electrical phenomena in living
  organisms

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Galvanic Cell
A Galvanic cell converts chemical energy into
electricity.
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Bacterial Fuel Cells
A microbial fuel cell converts chemical energy,
available in a bio-convertible substrate,
directly into electricity.
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• Advantages
• Electricity generation out of wastewater
• Glucose-poweredpacemakers
• Bio-sensors, and nutrient removal systems

• Disadvantages
• Power outputs - miliwats.
• Yet no commercially applications

80 electron efficiency
Finneran, K.T., Johnsen, C.V. Lovley, D.R. Int.
J. Syst. Evol. Microbiol. 53, 669673 (2003).
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Lymphocytes Immobilized on a Graphite Electrode
paraffin-impregnated graphite electrode
T-cells
Fluorescent image of cells attached to the
electrode.
reference electrode
counter electrode
Cyclic Voltammetry
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Electron Transport Catalyzed by a Redox Mediator
paraffin-impregnated graphite electrode
adsorbed redox mediator
reference electrode
counter electrode
Redox Mediator 2-palmytoilhydroquinone
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Catalytic Electron Transfer Mechanisms from
T-cells
H2Q
T-cells (reduced form)
ELECTRODE
2e-
T-cells (oxidized form)
Q
H2Q/Q - a redox catalyst
V. Mirceski et al. in press Clinical Chemistry
and Laboratory Medicine 
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Electrochemistry at a Single Cell Ultramicroelectr
odes
Image of a disk ultramicroelectrode by
electronic microscopy Typical dimensions within
the interval 10-6 to 10-9 m
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Exocytose of Neurotransmitters
Cartoon of a neuronal chemical synapse
Exocytose
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Amperometric 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 Microscopy
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Patch Clamp Ion Transfer through Cellular
Membranes
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Protein-Film Voltammetry
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Protein-Film and Cyclic Voltammetry
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Catalysis with Redox Active Enzymes

• 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

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Coupling of the Redox Chemistry with Ion Transfer
at Cellular Membranes
K
K
K channel complex that catalyzes a
redox reaction.
S. H. Heinemann et al. Science STCE, 2006, 350,
33.
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Voltammetry of Artificial Membranes Coupled
Electron-Ion Transfer Reaction
Edge Plane Pyrolytic Graphite Electrode
- e-
Organic electrolyte TBAX-
Organic film
Red
Ox
X-
Aqueous electrolyte CatX-
X-
Red(o) X-(aq) ? Ox(o) X-(o) e-
Reference electrode
Counter Electrode
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Role of the Transferring Ions on the Redox
Chemistry of the Membrane
SW voltammograms for the oxidation of a lutetium
complex in the nitrobenzene membrane
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Cholesterol Membrane at the LiquidLiquid
Interface
Edge Pyrolytic Graphite Electrode
-e
X-
Red
Ox
X-
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Monitoring of the Cholesterol Membrane Formation
with Cyclic Voltammetry
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Cholesterol Facilitates the Transfer kinetics of
ClO4-, NO3- and SCN-
NO3-
with cholesterol
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7.5
2.5
0
I / mA
-2.5
no cholesterol
-7.5
-10
-0.400
-0.200
0
0.100
0.300
0.400
E / V
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Q10 electrochemistry
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Q10 chemical transformation in a basic medium
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Caclium complexation with Q10-hydroxylated
derivatives
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Caclium complexation with Q10-hydroxylated
derivatives