1993 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)	松村功啓京都大学, 大学院・工学研究科, 助教授 (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 / 生物電気化学反応 / 修飾電極 / 分光電気化学 / 電解フッ素化 / トリフルオロエタノール / マイクロ電極 / 酵素反応
Research Abstract	1.メディエーター反応の解明と複合系への展開(長) 有機ニトロキシルオキシド(TEMPO)修飾ポリアクリル酸被覆グラファイト電極を用い、ラセミアルコール類のエナンチオ選択的酸化反応、ナフトール類の軸不斉選択的酸化反応を定量的に実現した。またフェロセン、ジアフォラーゼ、アルコールデヒドロゲナーゼ三元系の生物電気化学反応においてフェロセン残基のアルキル側鎖長のメディエーション反応に対する影響を検討し、NADH存在下アルコール類の選択的酸化反応を達成した。 2.生体機能分子の電極反応(谷口) ポリ-L-リジン,ポリ-L-オルニチンのポリペプチド修飾電極を用い、フェレドキシン-NADP^+リダクターゼ系によるNADP^+の還元反応の分光電気化学、電極挙動の解析を行った。またフェレドキシンとリンゴ酸酵素、グルタミン酸脱水素酵素またはイソクエン酸脱水素酵素の共役酵素反応をそれぞれの基質に対して実現した。 3.新しいメディエーター系の探索(宇根山、松村) 電気化学的還元で生成するセレノラート、ヘミアセタールからのアルデヒドと塩基、ポリフルオロ芳香族アニオンの3種メディエーターを調製しフッ素官能基の有機物への導入反応に活用するとともに、ペンタフルオロヨードベンゼンをメディエーターとするアルコール類の酸化反応を実現した(宇根山)。一方、2,2,2-トリフルオロエタノールが電極反応のすぐれた溶媒となることを見出した。この溶媒中でフェニルメチルスルフィドをメディエーターとする二級アルコールの高効率酸化反応を行った(松村)。 4.メディエーター反応の解明(末永) ジアフォラーゼ単分子膜の酵素活性を、フェロセニルメタノールまたはコバルト(II)トリフェナントロリン錯体とNADHの共存系でマイクロ電極(直径15μm)を用いて測定し、この手法は修飾酵素活性の評価法として使用できることを明らかにした。

Research Products
(27 results)

All Other

All Publications (27 results)

[Publications] Yoshitomo Kashiwagi: "Electrocatalytic Oxidative Coupling Reaction of Naphthols and Naphthol Ethers" Chemistry Letters. 81-84 (1993)
[Publications] Yoshitomo Kashiwagi: "Electrocatalytic Oxidative Coupling of Methylquinolines on TEMPO-Modified Graphite Felt Electrode" Chemistry Letters. 257-260 (1993)
[Publications] Yoshitomo Kashiwagi: "Electrocatalytic Oxidation of NADH on Thin Poly(acrylic acid)Film Coated Graphite Felt Electrode Coimmobilizing Ferrocene and Diaphorase" Chemistry Letters. 677-680 (1993)
[Publications] Iwao Suzuki: "Electrochemical Conversion of Alcohols into Aldehydes Mediated by Lipophilic γ-Cyclodextrin Bearing a Ferrocene Moiety" Chemistry Letters. 1719-1722 (1993)
[Publications] 長哲郎: "高分子修飾電極を用いる電解合成" 化学工業. 45. 121-126 (1994)
[Publications] Tetsuo Osa: "Electroenzymatic Oxidation of Alcohols on a Poly(acrylic acid)-coated Graphite Felt Electrode Terimmobilizing Ferrocene,Diaphorase and Alcohol Dehydrogenase" Chemistry Letters. 367-370 (1994)
[Publications] Masafumi Kobayasi: "Electrochemical Oxidation of 2-Substituted 3-N-(Arylamino)-4,4,4-trifluoro-2-butenate;An Access to 3-Substituted 2-Trifluoromethyl-3 H-indoles" Journal of Organic Chemistry. 59(印刷中). (1994)
[Publications] Kenji Uneyama: "Electrochemical Oxidation of N,N′-Disubstituted Trifluoroethanimidamides;An Approach to N-Substituted-2-trifluoromethylbenzimidazoles" Journal of Organic Chemistry. 59(印刷中). (1994)
[Publications] Isao Taniguchi: "Direct Electron Transfer of Ferredoxins at Indium Oxide Electrode in the Presence of Poly-L-lysine" Denki Kagaku. 61. 774-775 (1993)
[Publications] Isao Taniguchi: "Electrochemical Evaluation of the Surface Structures of Self-Assembling Promoter-modified Electrode for Protein Electrochemistry" Chemical Sensors Suppl.B.9. 239-242 (1993)
[Publications] Masato Tominaga: "Effect of Suface Hydrophylicity of an Indium Oxide Electrode on Direct Electron Transfer of Myoglobin" Chemistry Letters. 131-138 (1993)
[Publications] Isao Taniguchi: "Polypeptide Modified Indium Oxide Electrodes for Direct Electron Transfer of Ferredoxin" Journal of Chemical Society,Chemical Communications. 1994(印刷中). (1994)
[Publications] Isao Taniguchi: "Potential-Dependent Rectified Electron-Transfer at a Meldola's Blue Incorporated Decanethiol" Michrochemical Journal. 49(印刷中). (1994)
[Publications] 西山勝彦: "有機薄膜の電気化学" 信学技報. 93. 27-33 (1993)
[Publications] 谷口功: "生体分子の電気化学とその応用" 化学工業. 45. 252-257 (1994)
[Publications] 谷口功: "金属タンパク質の電子移動制御と電子機能素子の構築" 生物物理. 34(印刷中). (1994)
[Publications] Tomokazu Matsue: "Microring-ring Electrode for Manipulation of a Single Cell" Biochimica et Biophysica Acta. 1157. 332-335 (1993)
[Publications] Hiroshi Yamada: "Determination of Active Diaphorase Immobilized at Electrode Surfaces" Bioelectrochemistry and Bioenergetcs. 29. 337-346 (1993)
[Publications] Tomokazu Matsue: "Electrochemical Sensors Using Microarray Electrodes" Trends in Analytical Chemistry. 12. 100-108 (1993)
[Publications] Matsuhiko Nishizawa: "Fabrication of pH-Sensitive Microarray Electrode and Applicability to Biosensors" Sensors and Actuators. 13-14. 53-56 (1993)
[Publications] Hiroshi Yamada: "Electrn-Transfer at a Planar Lipid Membrane Incorporated with 7,7,8,8-Tetracyanoquinodimethane Studied By AC Impedance Spectroscopy" Journal of Physical Chemistry. 97. 9547-9549 (1993)
[Publications] Tomokazu Matsue: "Microamperometric Estimation of Photosynthesis Inhibition in a Single Protoplast" Biochemical and Biophysical Research Communications. 197. 1283-1287 (1993)
[Publications] Matsuhiko Nishizawa: "Surface Pretreatment for Electrochemical Fabrication of Ultrathin Patterned Conducting Polymers" Journal of Electrochemical Society. 140. 1650-1655 (1993)
[Publications] Yoshihiro Matsumura: "A New Reaction System for Efficient Electrochemical Oxidation of N-Methoxycarbonyl-2,2,2-trifluoroethylamines" Tetrahedron. 49. 8503-8512 (1993)
[Publications] Yoshihiro Matsumura: "A Convenient Route to β-Aryl-substituted Cyclic Enamines as Key Synthetic Intermadiates of Sceletium and Amaryllidaceae Alkaloids" Tetrahedron Letters. 35(印刷中). (1994)
[Publications] Isao Taniguchi: "Redox Mechanisms and Interfacial Properties of Molecules of Biological Importance" Direct Electron Transfer Reactions of Proteins at Functional Electrodes(The Electrochemical Society,Inc.,Pennigton,U.S.A.), 12 (1993)
[Publications] B.C.King: "Redox Mechanisms and Interfacial Properties of Molecules of Biological Importance" Myoglobin Electron Transfer and Ligand Binding Reactions(The Electrochemical Society,Inc.,Pennigton,U.S.A.), 10 (1993)

1993 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: "Electrocatalytic Oxidative Coupling Reaction of Naphthols and Naphthol Ethers" Chemistry Letters. 81-84 (1993)

[Publications] Yoshitomo Kashiwagi: "Electrocatalytic Oxidative Coupling of Methylquinolines on TEMPO-Modified Graphite Felt Electrode" Chemistry Letters. 257-260 (1993)

[Publications] Yoshitomo Kashiwagi: "Electrocatalytic Oxidation of NADH on Thin Poly(acrylic acid)Film Coated Graphite Felt Electrode Coimmobilizing Ferrocene and Diaphorase" Chemistry Letters. 677-680 (1993)

[Publications] Iwao Suzuki: "Electrochemical Conversion of Alcohols into Aldehydes Mediated by Lipophilic γ-Cyclodextrin Bearing a Ferrocene Moiety" Chemistry Letters. 1719-1722 (1993)

[Publications] 長哲郎: "高分子修飾電極を用いる電解合成" 化学工業. 45. 121-126 (1994)

[Publications] Tetsuo Osa: "Electroenzymatic Oxidation of Alcohols on a Poly(acrylic acid)-coated Graphite Felt Electrode Terimmobilizing Ferrocene,Diaphorase and Alcohol Dehydrogenase" Chemistry Letters. 367-370 (1994)

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

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

[Publications] Isao Taniguchi: "Direct Electron Transfer of Ferredoxins at Indium Oxide Electrode in the Presence of Poly-L-lysine" Denki Kagaku. 61. 774-775 (1993)

[Publications] Isao Taniguchi: "Electrochemical Evaluation of the Surface Structures of Self-Assembling Promoter-modified Electrode for Protein Electrochemistry" Chemical Sensors Suppl.B.9. 239-242 (1993)

[Publications] Masato Tominaga: "Effect of Suface Hydrophylicity of an Indium Oxide Electrode on Direct Electron Transfer of Myoglobin" Chemistry Letters. 131-138 (1993)

[Publications] Isao Taniguchi: "Polypeptide Modified Indium Oxide Electrodes for Direct Electron Transfer of Ferredoxin" Journal of Chemical Society,Chemical Communications. 1994(印刷中). (1994)

[Publications] Isao Taniguchi: "Potential-Dependent Rectified Electron-Transfer at a Meldola's Blue Incorporated Decanethiol" Michrochemical Journal. 49(印刷中). (1994)

[Publications] 西山勝彦: "有機薄膜の電気化学" 信学技報. 93. 27-33 (1993)

[Publications] 谷口功: "生体分子の電気化学とその応用" 化学工業. 45. 252-257 (1994)

[Publications] 谷口功: "金属タンパク質の電子移動制御と電子機能素子の構築" 生物物理. 34(印刷中). (1994)

[Publications] Tomokazu Matsue: "Microring-ring Electrode for Manipulation of a Single Cell" Biochimica et Biophysica Acta. 1157. 332-335 (1993)

[Publications] Hiroshi Yamada: "Determination of Active Diaphorase Immobilized at Electrode Surfaces" Bioelectrochemistry and Bioenergetcs. 29. 337-346 (1993)

[Publications] Tomokazu Matsue: "Electrochemical Sensors Using Microarray Electrodes" Trends in Analytical Chemistry. 12. 100-108 (1993)

[Publications] Matsuhiko Nishizawa: "Fabrication of pH-Sensitive Microarray Electrode and Applicability to Biosensors" Sensors and Actuators. 13-14. 53-56 (1993)

[Publications] Hiroshi Yamada: "Electrn-Transfer at a Planar Lipid Membrane Incorporated with 7,7,8,8-Tetracyanoquinodimethane Studied By AC Impedance Spectroscopy" Journal of Physical Chemistry. 97. 9547-9549 (1993)

[Publications] Tomokazu Matsue: "Microamperometric Estimation of Photosynthesis Inhibition in a Single Protoplast" Biochemical and Biophysical Research Communications. 197. 1283-1287 (1993)

[Publications] Matsuhiko Nishizawa: "Surface Pretreatment for Electrochemical Fabrication of Ultrathin Patterned Conducting Polymers" Journal of Electrochemical Society. 140. 1650-1655 (1993)

[Publications] Yoshihiro Matsumura: "A New Reaction System for Efficient Electrochemical Oxidation of N-Methoxycarbonyl-2,2,2-trifluoroethylamines" Tetrahedron. 49. 8503-8512 (1993)

[Publications] Yoshihiro Matsumura: "A Convenient Route to β-Aryl-substituted Cyclic Enamines as Key Synthetic Intermadiates of Sceletium and Amaryllidaceae Alkaloids" Tetrahedron Letters. 35(印刷中). (1994)

[Publications] Isao Taniguchi: "Redox Mechanisms and Interfacial Properties of Molecules of Biological Importance" Direct Electron Transfer Reactions of Proteins at Functional Electrodes(The Electrochemical Society,Inc.,Pennigton,U.S.A.), 12 (1993)

[Publications] B.C.King: "Redox Mechanisms and Interfacial Properties of Molecules of Biological Importance" Myoglobin Electron Transfer and Ligand Binding Reactions(The Electrochemical Society,Inc.,Pennigton,U.S.A.), 10 (1993)

長哲郎東北大学, 薬学部, 教授 (10010753)