Grant-in-Aid for Scientific Research on Priority Areas.
|Research Institution||Tohoku University|
OSA Tetsuo Tohoku University, Emeritus, Professor, 名誉教授 (10010753)
MATSUMURA Yoshihiro Nagasaki University, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (60026309)
MATSUE Tomokazu Tohoku University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (70173797)
TANIGUCHI Isao Kumamoto University, Faculty of Engineering, Professor, 工学部, 教授 (90112391)
UNEYAMA Kenji Okayama University, Faculty of Engineering, Professor, 工学部, 教授 (00033150)
|Project Fiscal Year
1993 – 1995
Completed(Fiscal Year 1996)
|Budget Amount *help
¥92,300,000 (Direct Cost : ¥92,300,000)
Fiscal Year 1995 : ¥21,300,000 (Direct Cost : ¥21,300,000)
Fiscal Year 1994 : ¥25,000,000 (Direct Cost : ¥25,000,000)
Fiscal Year 1993 : ¥46,000,000 (Direct Cost : ¥46,000,000)
|Keywords||Mediator reaction / Bioelectrocatalytic reaction / Mediator-modified electrode / Mediator- and enzyme-multimodified electrode / ferredoxin / Fluoroselenation / Oxidative coupling / Scanning electrochemical microscopy / メディエーター反応 / 電気化学的酵素触媒反応 / メディエーター修飾電極 / メディエーター-酵素複合修飾電極 / フェレドキシン / フルオロセレノ化反応 / 酸化二量化 / 走査型電気化学顕微鏡 / キラルメディエーター修飾電極 / メディエーター酵素複合修飾電極 / フルオロフェニルセレニド / 電極還元活性塩基 / 癌胎児性抗原 / 修飾電極 / エナンチオ選択的反応 / 生物電気化学反応器 / 分光電気化学 / トリフルオロエタノール / 電解フッ素化 / 酵素マイクロパターン / 生物電気化学反応 / マイクロ電極 / 酵素反応|
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
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.