RESUMEN

An intrinsic self-charging biosupercapacitor built on a unique concept for the fabrication of biodevices based on redox polymers is presented. The biosupercapacitor consists of a high-potential redox polymer based bioanode and a low-potential redox polymer based biocathode in which the potentials of the electrodes in the discharged state show an apparent potential mismatch Eanode >Ecathode and prevent the use of the device as a conventional biofuel cell. Upon charging, the potentials of the electrodes are shifted to more positive (cathode) and more negative (anode) values because of a change in the aox -to-ared ratio within the redox polymer matrix. Hence, a potential inversion occurs in the charged state (Eanode 0.4 V is achieved and the biodevice acts as a true biosupercapacitor. The bioanode consists of a novel specifically designed high-potential Os complex modified polymer for the efficient immobilization and electrical wiring of glucose converting enzymes, such as glucose oxidase and flavin adenine dinucleotide (FAD)-dependent glucose dehydrogenase. The cathodic side is constructed from a low-potential Os complex modified polymer integrating the O2 reducing enzyme, bilirubin oxidase. The large potential differences between the redox polymers and the prosthetic groups of the biocatalysts ensure fast and efficient charging of the biodevice.

RESUMEN

We propose the very first "Nernstian biosupercapacitor", a biodevice based on only one redox polymer: poly(vinyl imidazole-co-allylamine)[Os(bpy)2 Cl], and two biocatalysts. At the bioanode PQQ-dependent glucose dehydrogenase reduces the Os3+ moieties at the polymer to Os2+ shifting the Nernst potential of the Os3+ /Os2+ redox couple to negative values. Concomitantly, at the biocathode the reduction of O2 by means of bilirubin oxidase embedded in the same redox polymer leads to the oxidation of Os2+ to Os3+ shifting the Nernst potential to higher values. Despite the use of just one redox polymer an open circuit voltage of more than 0.45 V was obtained during charging and the charge is stored in the redox polymer at both the bioanode and the biocathode. By connecting both electrodes via a predefined resistor a high power density is obtained for a short time exceeding the steady state power of a corresponding biofuel cell by a factor of 8.

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RESUMEN

Phenothiazine-modified redox hydrogels were synthesized and used for the wiring of the aldehyde oxidoreductase PaoABC to electrode surfaces. The effects of the pH value and electrode surface modification on the biocatalytic activity of the layers were studied in the presence of vanillin as the substrate. The enzyme electrodes were successfully employed as bioanodes in vanillin/O2 biofuel cells in combination with a high potential bilirubin oxidase biocathode. Open circuit voltages of around 700 mV could be obtained in a two compartment biofuel cell setup. Moreover, the use of a rather hydrophobic polymer with a high degree of crosslinking sites ensures the formation of stable polymer/enzyme films which were successfully used as bioanode in membrane-less biofuel cells.

Asunto(s)

RESUMEN

Benzoxazine-based redox polymers bearing Os complexes are synthesized and used as an immobilization matrix for glucose oxidase (GOx) as a model system for a reagentless biosensor. The polymers are formed by electrochemically induced anodic polymerization of the corresponding benzoxazine monomers modified with Os complexes. The precursors are synthesized in a Mannich-type reaction between bisphenol A, formaldehyde, and the corresponding Os complexes or ligands, which contain free amino groups. The Os complexes are redox active within the polymer films, and thus, can be used as redox relays for the electron transfer between the electrode surface and the prosthetic group within the enzyme. Entrapment of GOx within the poly(benzoxazine) film is achieved successfully, as shown by the biocatalytic activity of the poly(benzoxazine)/GOx films upon the addition of glucose.