Development of Mediator Reaction

1.介体修饰电极、介体修饰电极和酶修饰电极上的立体选择性有机合成。固定化介体、酶和/或辅酶对多种有机化合物进行了对映体选择性和电催化(电酶)反应。实际上，不仅在手性碱和非手性碱的存在下，手性TEMPO修饰电极和手性TEMPO修饰电极上实现了制备氧化，而且酶-多修饰电极上的制备氧化和还原也以高对映选择性、高电流效率和高转化率进行。2.以铁氧还蛋白为介体的生物电化学转化(谷口)还原铁还蛋白…此外，具有阳离子表面的功能修饰电极已被成功地用作电子传递媒介，通过铁还蛋白-NADP+还原酶开发了各种新的生物电催化反应。例如，有效地生产了L-谷氨酸和L-苹果酸。利用定点突变技术，研究了氨基酸在铁氧还蛋白中的作用。3.新介体体系的建立建立了一种新的电化学法进行氟功能化。二苯二硒的电氧化和还原生成苯硒。氟化物和苯硒酸酯分别有效地促进了烯烃的氟硒化和二氟甲基硒化反应(UNYAMA)。开发了一种新的电化学氧化体系和一种新的中介体系，用于高效氧化难氧化有机物。还发现了一个由电化学生成的碱与碘分子组成的反应体系，适合于C2对称化合物的立体选择性合成和不对称氧化偶联(MatSumura)。4.中介反应分析(MATSUE)通过对中介反应的定量分析，确定了一些氧化还原酶的动力学参数。用扫描电化学显微镜(SECM)对定域介体过程进行了表征。SECM技术与免疫分析系统相结合，用于痕量生物分析。较少

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