Development of Mediator Reaction

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Investigation of this group extended modiator reactions for electrocatalytic synthesis of organic compounds, together with dynamic and static analysis of electron transfer mechanism and processes.1.Stereoselective Electroorganic Synthesis on Mediator-modified Electrodes and Mediator-and Enzyme-multimodified Electrodes (OSA) Poly (acrylic acid) -coating graphite felt electrodes immobilizing mediator, enzme and/or co-enzyme have developed enantioselective and electrocatalytic (electroenzymatic) reactions for several types of organic compounds. Actually, the preparative oxidations have not only been achieved on the achiral TEMPO-modified and chiral TEMPO-modified electrodes in the presence of chiral base and achiral base, respectively, but the preparative oxidations and reductions also done on the enzyme-multimodified electrodes in high enantioselectivity, high current efficiency and high conversion.2.Bioelectrochemical Conversion with Ferredoxin as Mediator (TANIGUCHI) Reduced ferredoxin … More at the functional modified electrodes possessing a cationic surface has been successfuly used as an electron transfer mediator to develop various new bioelectrocatalytic reactions via ferredoxin-NADP+ -reductase as in nature. For example, L-glutamic acid and L-malic acid were effectively produced. Using site-directed mutagenetic techniques, functions of amino acids in ferredoxin have also been studied.3.Creation of New Mediator systems (UNEYAMA and MATSUMURA) A new electrochemical method for fluoro-functionalization has been developed. Electro-oxidation and reduction of diphenyl diselenide generate benzene seleneny. Ifluoride and benzene selenate which mediate efficiently fluoro-selenation and difluoromethyl-selenation of olefins, respectively (UNEYAMA). A new electrochemical oxidation system and a new mediatory system have been exploited for highly efficient oxidation of hardly oxidizable organic compounds. A reaction system consisting of electrochemically generated base has also been found with iodine molecule, which was suitable to a stereoselective synthesis of C2-symmetric compounds and an asymmetric oxidative coupling (MATSUMURA).4.Analysis of Mediator Reactions (MATSUE) The kinetic parameters of some redox enzymes have been determined by quantitative analyzes of mediator reactions. A scanning electrochemical microscopy (SECM) has been fabricated for characterization of localized mediator processes. The SECM technique was combined with immunoassay system for trace bioanalysis. Less