Hydrogenase electrodes for fuel cells.

Considering crucial problems that limit use of platinum-based fuel cells, i.e. cost and availability, poisoning by fuel impurities and low selectivity, we propose electrocatalysis by enzymes as a valuable alternative to noble metals. Hydrogenase electrodes in neutral media achieve hydrogen equilibrium potential (providing 100% energy conversion), and display high activity in H(2) electrooxidation, which is similar to that of Pt-based electrodes in sulphuric acid. In contrast with platinum, enzyme electrodes are highly selective for their substrates, and are not poisoned by fuel impurities. Hydrogenase electrodes are capable of consuming hydrogen directly from microbial media, which ensures their use as fuel electrodes in treatment of organic wastes.

Polyaniline-modified cholinesterase sensor for pesticide determination.

Cholinesterase sensors based on glassy carbon and planar epoxy graphite electrodes modified with processed polyaniline have been developed and examined for pesticide detection. The modification of electrode surface with polyaniline provides high operational stability and sensitivity towards the pesticides investigated. The detection limits found (coumaphos, 0.002, trichlorfon, 0.04, aldicarb, 0.03, methiocarb, 0.08 mg l(-1)) make it possible to detect the pollutants in the waters on the level of limited threshold levels without sample preconcentration.

Direct and electrically wired bioelectrocatalysis by hydrogenase from Thiocapsa roseopersicina.

Hydrogen enzyme electrodes based on direct and mediated bioelectrocatalysis were developed. Direct bioelectrocatalysis of hydrogen oxidation/evolution was observed for hydrogenase adsorbed on carbon filament material. The equilibrium hydrogen potential was achieved on mediatorless hydrogen enzyme electrodes in hydrogen atmosphere. The electrocatalytic activity of hydrogenase in direct bioelectrocatalysis of hydrogen oxidation was two orders of magnitude higher compared to platinum. The reported electrode remained 50% activity after 6 months of storage with periodical testing. Wired bioelectrocatalysis was achieved by adsorption of hydrogenase onto electropolymerized redox mediator N-methyl-N'-(12-pyrrol-1-yl-dodecyl)-4,4'-bipyridinium ditetrafluoroborate.

Amperometric biosensor for glutamate using prussian blue-based "artificial peroxidase" as a transducer for hydrogen peroxide.

The specially deposited Prussian Blue denoted as "artificial peroxidase" was used as a transducer for hydrogen peroxide. The electrocatalyst was stable, highly active, and selective to hydrogen peroxide reduction in the presence of oxygen, which allowed sensing of H2O2 around 0.0 V (Ag/AgCl). Glutamate oxidase was immobilized on the surface of the Prussian Blue-modified electrode in a Nafion layer using a nonaqueous enzymology approach. The calibration range for glutamate in flow injection system was 1 x 10(-7)-1 x 10(-4) M. The lowest concentration of glutamate detected (1 x 10(-7) M) and the highest sensitivity in the linear range of 0.21 A M-1 cm-2 were achieved. The influence of reductants was practically avoided using the low potential of an indicator electrode (0.0 V Ag/AgCl). The attractive performance characteristics of the glutamate biosensor illustrate the advantages of Prussian Blue-based "artificial peroxidase" as transducer for hydrogen peroxide detection.

Processible polyaniline as an advanced potentiometric pH transducer. Application to biosensors.

An advanced potentiometric pH transducer based on processible polyaniline (PCPAn) is reported on. Both glassy carbon and screen-printed carbon electrodes modified with PCPAn by dip-coating exhibited a fully reversible potentiometric response of approximately 90 mV/pH unit over the range from pH 3 to 9. Such a significantly higher potentiometric response of PCPAn-modified electrodes as compared with those of existing devices is explained on the basis of the thermodynamics of polyaniline redox reactions. The PCPAn-based pH transducers exhibit both good operational stability and prolonged shelf life and display a negligible response toward singly charged cations. The new thick-film pH transducer was employed for designing a potentiometric biosensor for urea. In the model solution which mimics blood serum, the urea-sensitive electrode has a detection limit of 10(-5) M urea and a maximum response of approximately 120 mV. The attractive performance characteristics are advantageous over those of existing pH sensors and offer great promise for sensing and biosensing applications.

Non-aqueous enzymology approach for improvement of reagentless mediator-based glucose biosensor.

The formation of Nafion membranes containing glucose oxidase and dimethylferrocene as a mediator was optimized using a previously reported non-aqueous enzymology approach for biosensor development. Enzyme immobilization in Nafion membranes was carried out from water-organic mixtures with a high content of organic solvent. The mediator based reagentless glucose electrode was tested in a flow injection system. The response towards glucose addition was stable: the reproducibility during 50 assays exceeded 95%. The response was linear over the glucose concentration range 0.5-50 mM.

Prussian-Blue-based amperometric biosensors in flow-injection analysis.

Optimisation of the electrodeposition of Prussian Blue onto mirrored glassy carbon electrodes yielded a modified electrode practically insensitive to oxygen reduction. At the same time the electrode activity towards hydrogen peroxide reduction was extremely high. This allowed the detection of hydrogen peroxide by electroreduction over a wide potential range. Flow-injection investigations of this electrode inserted into a flowthrough electrochemical cell of the confined wall-jet type showed that the response for hydrogen peroxide is limited by diffusion. Glucose and alcohol biosensors were made by immobilisation of glucose oxidase and alcohol oxidase respectively, within a Nafion layer, onto the top of the Prussian-Blue-modified electrodes. By increasing the density of Nafion and decreasing the measuring potential the glucose biosensor was made completely insensitive to both ascorbate and acetominophes.