Fabien Giroud

Single Glucose Biofuel Cells Implanted in Rats Power Electronic Devices

We describe the first implanted glucose biofuel cell (GBFC) that is capable of generating sufficient power from a mammals body fluids to act as the sole power source for electronic devices. This GBFC is based on carbon nanotube/enzyme electrodes, which utilize glucose oxidase for glucose oxidation and laccase for dioxygen reduction. The GBFC, implanted in the abdominal cavity of a rat, produces an average open-circuit voltage of 0.57 V. This implanted GBFC delivered a power output of 38.7 μW, which corresponded to a power density of 193.5 μW cm−2 and a volumetric power of 161 μW mL−1. We demonstrate that one single implanted enzymatic GBFC can power a light-emitting diode (LED), or a digital thermometer. In addition, no signs of rejection or inflammation were observed after 110 days implantation in the rat.

Hydrogen peroxide produced by glucose oxidase affects the performance of laccase cathodes in glucose/oxygen fuel cells: FAD-dependent glucose dehydrogenase as a replacement

Hydrogen peroxide production by glucose oxidase (GOx) and its negative effect on laccase performance have been studied. Simultaneously, FAD-dependent glucose dehydrogenase (FAD-GDH), an O2-insensitive enzyme, has been evaluated as a substitute. Experiments focused on determining the effect of the side reaction of GOx between its natural electron acceptor O2 (consumed) and hydrogen peroxide (produced) in the electrolyte. Firstly, oxygen consumption was investigated by both GOx and FAD-GDH in the presence of substrate. Relatively high electrocatalytic currents were obtained with both enzymes. O2 consumption was observed with immobilized GOx only, whilst O2 concentration remained stable for the FAD-GDH. Dissolved oxygen depletion effects on laccase electrode performances were investigated with both an oxidizing and a reducing electrode immersed in a single compartment. In the presence of glucose, dramatic decreases in cathodic currents were recorded when laccase electrodes were combined with a GOx-based electrode only. Furthermore, it appeared that the major loss of performance of the cathode was due to the increase of H2O2 concentration in the bulk solution induced laccase inhibition. 24 h stability experiments suggest that the use of O2-insensitive FAD-GDH as to obviate in situ peroxide production by GOx is effective. Open-circuit potentials of 0.66 ± 0.03 V and power densities of 122.2 ± 5.8 μW cm(-2) were observed for FAD-GDH/laccase biofuel cells.

Impedimetric immunosensor based on a polypyrrole-antibiotic model film for the label-free picomolar detection of ciprofloxacin.

This paper describes the construction of an impedimetric immunosensor for the label-free detection of ciprofloxacin, an antibiotic belonging to synthetic fluoroquinolones. A poly(pyrrole-N-hydroxysuccinimide) film was electrogenerated onto electrodes and then used for the reagentless covalent binding of a fluoroquinolone model bearing an amino group. The resulting electrodes were utilized to immobilize a layer of anticiprofloxacin antibody onto the polymer surface by immunoreaction. In presence of ciprofloxacin, the antibody was displaced in solution inducing marked changes in the impedance of the sensor electrodes. These phenomena were detected and characterized by electrochemical impedance spectroscopy allowing the selective detection of extremely low ciprofloxacin concentration, namely, 1 x 10(-12) g mL(-1) or 3 pmol L(-1). Sensors exposed to ciprofloxacin showed a decrease in the sum of the interfacial resistances with the increase in ciprofloxacin concentration from 1 x 10(-12) to 1 x 10(-6) g mL(-1).

Hybrid enzymatic and organic electrocatalytic cascade for the complete oxidation of glycerol.

We demonstrate the complete electrochemical oxidation of the biofuel glycerol to CO2 using a hybrid enzymatic and small-molecule catalytic system. Combining an enzyme, oxalate oxidase, and an organic oxidation catalyst, 4-amino-TEMPO, we are able to electrochemically oxidize glycerol at a carbon electrode, while collecting up to as many as 16 electrons per molecule of fuel. Additionally, we investigate the anomalous electrocatalytic properties that allow 4-amino-TEMPO to be active under the acidic conditions that are required for oxalate oxidase to function.

Membraneless glucose/O2 microfluidic enzymatic biofuel cell using pyrolyzed photoresist film electrodes

Biofuel cells typically yield lower power and are more difficult to fabricate than conventional fuel cells using inorganic catalysts. This work presents a glucose/O2 microfluidic biofuel cell (MBFC) featuring pyrolyzed photoresist film (PPF) electrodes made on silicon wafers using a rapid thermal process, and subsequently encapsulated by rapid prototyping techniques into a double-Y-shaped microchannel made entirely of plastic. A ferrocenium-based polyethyleneimine polymer linked to glucose oxidase (GOx/Fc-C6-LPEI) was used in the anode, while the cathode contained a mixture of laccase, anthracene-modified multi-walled carbon nanotubes, and tetrabutylammonium bromide-modified Nafion (MWCNTs/laccase/TBAB-Nafion). The cell performance was studied under different flow-rates, obtaining a maximum open circuit voltage of 0.54 ± 0.04 V and a maximum current density of 290 ± 28 μA cm(-2) at room temperature under a flow rate of 70 μL min(-1) representing a maximum power density of 64 ± 5 μW cm(-2). Although there is room for improvement, this is the best performance reported to date for a bioelectrode-based microfluidic enzymatic biofuel cell, and its materials and fabrication are amenable to mass production.

Redox-active glyconanoparticles as electron shuttles for mediated electron transfer with bilirubin oxidase in solution

We demonstrate self-assembly, characterization and bioelectrocatalysis of redox-active cyclodextrin-coated nanoparticles. The nanoparticles with host-guest functionality are easy to assemble and permit entrapment of hydrophobic redox molecules in aqueous solution. Bis-pyrene-ABTS encapsulated nanoparticles were investigated electrochemically and spectroscopically. Their use as electron shuttles is demonstrated via an intraelectron transfer chain between neighboring redox units of clustered particles (Dh,DLS = 195 nm) and the mono- and trinuclear Cu sites of bilirubin oxidases. Enhanced current densities for mediated O2 reduction are observed with the redox nanoparticle system compared to equivalent bioelectrode cells with dissolved mediator. Improved catalytic stability over 2 days was also observed with the redox nanoparticles, highlighting a stabilizing effect of the polymeric architecture. Bioinspired nanoparticles as mediators for bioelectrocatalysis promises to be valuable for future biofuel cells and biosensors.