Modified poly dehydrogenase electrode

All potentials vs. screen-printed pseudo Ag/AgCl reference, except values marked with double-dagger (J), which are vs. screen-printed Ag/Pd, and 02 those marked with asterisk ( ), which are vs. Ag/3M AgCl double-junction reference electrode. Abbreviations LDH lactate dehydrogenase, LOD lactate oxidase, PVA-SbQ styrlpyridinium-modified poly(vinyl alcohol), FIA flow injection analysis. aLinear ranges using a dialysis system. 

New developments in this area include uric acid sensors based on the mediation of urate oxidase by a novel redox polymer, poly(N-methyl-o-phenylenediamine) [145], and by the freely diffusing mediator 1-methoxy-5-methylphenazinium [146], continued research on the direct amperometric detection of NADH [147] and the use of redox mediators [148] for dehydrogenase enzymes, to allow practical sensors that exploit this large class of enzymes, and the use of cytochrome P450-modified glassy carbon electrodes as drug metabolism biosensors [149]. 

Karyakin AA, Karyakina EE, Schuhmann W, Schmidt HL, Varfolomeyev SD. New amperometric dehydrogenase electrodes based on electrocatalytic NADH-oxidation at poly (methylene blue)-modified electrodes. Electroanalysis 1994 6 821-829. 

Several approaches have been undertaken to construct redox active polymermodified electrodes containing such rhodium complexes as mediators. Beley [70] and Cosnier [71] used the electropolymerization of pyrrole-linked rhodium complexes for their fixation at the electrode surface. An effective system for the formation of 1,4-NADH from NAD+ applied a poly-Rh(terpy-py)2 + (terpy = terpyridine py = pyrrole) modified reticulated vitreous carbon electrode [70]. In the presence of liver alcohol dehydrogenase as production enzyme, cyclohexanone was transformed to cyclohexanol with a turnover number of 113 in 31 h. However, the current efficiency was rather small. The films which are obtained by electropolymerization of the pyrrole-linked rhodium complexes do not swell. Therefore, the reaction between the substrate, for example NAD+, and the reduced redox catalyst mostly takes place at the film/solution interface. To obtain a water-swellable film, which allows the easy penetration of the substrate into the film and thus renders the reaction layer larger, we used a different approach. Water-soluble copolymers of substituted vinylbipyridine rhodium complexes with N-vinylpyrrolidone, like 11 and 12, were synthesized chemically and then fixed to the surface of a graphite electrode by /-irradiation. The polymer films obtained swell very well in aqueous... 

Modified electrodes for this analytical purpose have mostly been formed by electrode adsorption of the mediator systems on the electrode surface or by electropolymerization [24,116]. Recently, for example, NAD(P)H oxidations have been performed on platinum or gold electrodes modified with a monolayer of pyrroloquinoline quinone (PQQ) [117] or on poly(methylene blue)-modified electrodes with different dehydrogenases entrapped in a Nafion film for the amperometric detection of glucose, lactate, malate, or ethanol [118]. In another approach, carbon paste electrodes doped with methylene green or meldola blue together with diaphorase were used for the NADH oxidation [119]. A poly(3-methylthio-phene) conducting polymer electrode was efficient for the oxidation of NADH [120]. By electropolymerization of poly(aniline) in the presence of poly(vinylsulfonate) counterions. 

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