1994 Fiscal Year Annual Research Report

メディエーター反応の展開

Research Project

Project/Area Number	05235102
Research Institution	Tohoku University
Principal Investigator	長哲郎東北大学, 薬学部, 教授 (10010753)
Co-Investigator(Kenkyū-buntansha)	松村功啓長崎大学, 薬学部, 教授 (60026309) 末永智一東北大学, 工学部, 助教授 (70173797) 谷口功熊本大学, 工学部, 教授 (90112391) 宇根山健治岡山大学, 工学部, 教授 (00033150)
Keywords	メディエーター反応 / 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
Research Abstract	1.メディエーター修飾電極による高選択的有機合成反応(長) TEMPO修飾グラファイトフェルト電極を用いたナフトール類のエナンチオ選択的カップリング反応を(-)-スパルティンの存在下成功させた。2.-ナフトールからはエナンチオ選択率99%、単離収率93%でS-ビナフチル体を与えた。フェロセン、ジアフォラーゼ、NADH、アルコールデヒドロゲナーゼの4元系修飾電極を作製し、完全な生物電気化学反応器を構築した。 2.生体機能的メディエーターの創成と分子変換(谷口) 金属タンパク質の電子移動制御のための電極界面機能を定量的に解明した。特に修飾酸化インジウム電極によるフェレドキシンをメディエーターとする酸素触媒反応を実現し、電極の光透過性を利用して円偏光二色性スペクトルなどの分光電気化学的手法を反応機構解明に用いた。 3.新しいメディエーター系の創成(宇根山、松村) 電気化学的ジフルオロブロモメチル-セレネニル化反応、電気化学的フルオロ-セレネニル化反応などを実現する新しいメディエーター系を創製し、フッ素化学への応用を展開した(宇根山)。2,2,2-トリフルオロエタノールを溶媒としフェニルメチルスルフィドをメディエーターとした2-オクタノールの電気化学的触媒酸化反応、ヨードイオンをメディエーターとするアルデヒドの酸化的官能基変換とδ-アミノレブリン酸およびその同族体の合成など新しいメディエーター系を創成した(松村)。メディエーター反応の特質の解明(末永) 超微小電極による極微物質の酵素触媒反応を解明するため、走査型電気化学顕微鏡を用いた酵素マイクロパターンの作製、その表面の画像化などによる解析を行った。

Research Products

(15 results)

All Other

All Publications (15 results)

[Publications] Yoshitomo Kashiwagi: "The Effects of Chain Length of Ferrocene Moiety on Mediator-and Enzymes-Modified Electrode" Denki Kagaku. 62. 1240-1246 (1994)
[Publications] Tetsuo Osa: "Enantioselective,Electrocatalytic Oxidative Couplings of Naphthols,Naphthyl Ether and Phenanthrol on a TEMPO-Modified Graphite Fell Electrode in the Presence of (-)-Sparteine" Journal of Chemical Society,Chemical Communications. 2535-2537 (1994)
[Publications] Masafumi Kobayasi: "Electrochemical Oxidation of 2-Substituted3-N-(Arylamino)-4,4,4-trifluoro-2-butenate;An Access to 3-Substituted 2-Trifluoromethyl-3H-indoles" Journal of Organic Chemistry. 59. 1909-1911 (1994)
[Publications] Kenji Uneyama: "Electrochemical Oxidation of N,N-Disubstituted Trifluoroethanimidamides;An Approach to N-Substituted-2-trifluoromethylbenzimidazoles" Journal of Organic Chemistry. 59. 3003-3014 (1994)
[Publications] Kenji Uneyama: "Electrochemical Generation of Trifluoroacetaldehyde from its Hemiacetal and Aldol Reaction with Active Methylene Compounds" Denki Kagaku. 62. 1151-1153 (1994)
[Publications] Katsuhiko Nishiyama: "Aminosilane Modified Indium Oxide Electrodes for Direct Electron Transfer of Ferrodoxin" Journal of Electroanalytical Chemistry. 373. 255-258 (1994)
[Publications] Isao Taniguchi: "In Situ Circular Dichrosim Spestroelectrochemistry of Spinach Ferredoxin Using a Promoter Modified Indium Oxide Electrode" Denki Kagaku. 62. 985-986 (1994)
[Publications] Hiroshi Yamada: "Microvoltammetric Characterization of Diaphorase Monolayer at Glass Surfaces" Bioelectrochemistry and Bioenergetcs. 33. 91- (1994)
[Publications] Tomokazu Matsue: "Pemselectivity of Voltage-Gated Alamethicin Ion Channel Studied by Microamperometry" Journal of Physical Chemistry. 98. 11001-11003 (1994)
[Publications] Yukihiro Miwa: "Electrocatalytic Oxidation of Alcohols a Polypyrrole Diaphragm Electrode Immobilized with Diaphorase and Alcohol Dehydrogenase" Denki Kagaku. 62. 1256-1257 (1994)
[Publications] Hitoshi Shiku: "Microfabrication and Characterization of Diaphorase-Patterned Surfaces by Scanning Electrochemical Microscopy" Analytical Chemistry. 67. 312-317 (1995)
[Publications] Yoshihiro Matsumura: "A Convenient Method for Introducing Oxo Group into the β-Position of Cyclic Amines and Its Application to Synthesis of δ-Aminolevulinic Acid" Bulletin of the Chemical Society of Japan. 67. 304-306 (1994)
[Publications] Yoshihiro Matsumura: "First Synthesis of Optically Pure α-Amino Amine as Asymmetric Amino Transfer Reagent and its Use in Asymmetric Mannich Reaction" Tetrahedron Letters. 35. 3737-3740 (1994)
[Publications] Yoshihiro Matsumura: "Selective Bond Cleavage of Borneol and Related Alcohols by Electrochemical Oxidation" Denki Kagaku. 62. 1154-1157 (1994)
[Publications] Naoki Kise: "Diastereoselective Synthesis of Anti-and Syn-3-Amino-2-Hydroxylakanoic Acid Derivatives" Tetrahedron Letters. 36. 909-912 (1995)

1994 Fiscal Year Annual Research Report

メディエーター反応の展開

Principal Investigator

長 哲郎 東北大学, 薬学部, 教授 (10010753)

Research Products

[Publications] Yoshitomo Kashiwagi: "The Effects of Chain Length of Ferrocene Moiety on Mediator-and Enzymes-Modified Electrode" Denki Kagaku. 62. 1240-1246 (1994)

[Publications] Tetsuo Osa: "Enantioselective,Electrocatalytic Oxidative Couplings of Naphthols,Naphthyl Ether and Phenanthrol on a TEMPO-Modified Graphite Fell Electrode in the Presence of (-)-Sparteine" Journal of Chemical Society,Chemical Communications. 2535-2537 (1994)

[Publications] Masafumi Kobayasi: "Electrochemical Oxidation of 2-Substituted3-N-(Arylamino)-4,4,4-trifluoro-2-butenate;An Access to 3-Substituted 2-Trifluoromethyl-3H-indoles" Journal of Organic Chemistry. 59. 1909-1911 (1994)

[Publications] Kenji Uneyama: "Electrochemical Oxidation of N,N-Disubstituted Trifluoroethanimidamides;An Approach to N-Substituted-2-trifluoromethylbenzimidazoles" Journal of Organic Chemistry. 59. 3003-3014 (1994)

[Publications] Kenji Uneyama: "Electrochemical Generation of Trifluoroacetaldehyde from its Hemiacetal and Aldol Reaction with Active Methylene Compounds" Denki Kagaku. 62. 1151-1153 (1994)

[Publications] Katsuhiko Nishiyama: "Aminosilane Modified Indium Oxide Electrodes for Direct Electron Transfer of Ferrodoxin" Journal of Electroanalytical Chemistry. 373. 255-258 (1994)

[Publications] Isao Taniguchi: "In Situ Circular Dichrosim Spestroelectrochemistry of Spinach Ferredoxin Using a Promoter Modified Indium Oxide Electrode" Denki Kagaku. 62. 985-986 (1994)

[Publications] Hiroshi Yamada: "Microvoltammetric Characterization of Diaphorase Monolayer at Glass Surfaces" Bioelectrochemistry and Bioenergetcs. 33. 91- (1994)

[Publications] Tomokazu Matsue: "Pemselectivity of Voltage-Gated Alamethicin Ion Channel Studied by Microamperometry" Journal of Physical Chemistry. 98. 11001-11003 (1994)

[Publications] Yukihiro Miwa: "Electrocatalytic Oxidation of Alcohols a Polypyrrole Diaphragm Electrode Immobilized with Diaphorase and Alcohol Dehydrogenase" Denki Kagaku. 62. 1256-1257 (1994)

[Publications] Hitoshi Shiku: "Microfabrication and Characterization of Diaphorase-Patterned Surfaces by Scanning Electrochemical Microscopy" Analytical Chemistry. 67. 312-317 (1995)

[Publications] Yoshihiro Matsumura: "A Convenient Method for Introducing Oxo Group into the β-Position of Cyclic Amines and Its Application to Synthesis of δ-Aminolevulinic Acid" Bulletin of the Chemical Society of Japan. 67. 304-306 (1994)

[Publications] Yoshihiro Matsumura: "First Synthesis of Optically Pure α-Amino Amine as Asymmetric Amino Transfer Reagent and its Use in Asymmetric Mannich Reaction" Tetrahedron Letters. 35. 3737-3740 (1994)

[Publications] Yoshihiro Matsumura: "Selective Bond Cleavage of Borneol and Related Alcohols by Electrochemical Oxidation" Denki Kagaku. 62. 1154-1157 (1994)

[Publications] Naoki Kise: "Diastereoselective Synthesis of Anti-and Syn-3-Amino-2-Hydroxylakanoic Acid Derivatives" Tetrahedron Letters. 36. 909-912 (1995)

長哲郎東北大学, 薬学部, 教授 (10010753)