1998 Fiscal Year Annual Research Report

活性酸素種の生成・検出・反応制御に関する電気化学的アプローチ

Research Project

Project/Area Number	10305064
Research Category	Grant-in-Aid for Scientific Research (A)
Research Institution	Tokyo Institute of Technology
Principal Investigator	大坂武男東京工業大学, 大学院・総合理工学研究科, 教授 (80152099)
Co-Investigator(Kenkyū-buntansha)	北村房男東京工業大学, 大学院・総合理工学研究科, 助手 (00224973) 岡島武義東京工業大学, 大学院・総合理工学研究科, 助手 (70194347) 徳田耕一東京工業大学, 大学院・総合理工学研究科, 教授 (40016548)
Keywords	活性酸素種 / 酸素ラジカル / ストップドフロー分光法 / スーパーオキシドイオン / 過酸化水素 / 酵素 / 酸素 / 電気化学
Research Abstract	本研究では,様々な生命現象に密接に関連している活性酸素種(スーパーオキシドイオンO_2,過酸化水素H_2O_2,ヒドロペルオキシラジカルHO_2・,ヒドロキシルラジカル・OHなど)の電解生成,in situ検出,反応制御,反応特異性の解明を目的として行われ,本年度は次の成果を得た。 1. レドックス酵素の単分子層を電極表面に自己組織化することによって酵素配向電極を構築し,これを用いてO_2の電気化学的検出に成功した。 2. 新規環状金属錯体の自己組織化単分子膜(SAM)修飾電極を構築し,このSAM電極のH_2O_2のO_2への特異な電極酸化触媒能を見い出し,そのメカニズムをin situ分光電気化学法で解明した。 3. 非水溶媒中,吊り下げ水銀電極でO_2/O_2レドックス対の電極反応において電流振動現象が起こることをはじめて見い出し,その可能なメカニズムを提案した。新規な電気化学界面振動現象を明らかした。 4. OHラジカルの電解生成系を提案した。O_2と生体関連物質との反応特異性をストップドフロー分光法で解明した。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] Y.CHE: "New Oscillatory Phenomena in the Redox Reaction of O_2/O_2-Couple on Hanging Mercury Drop Electrode in Acetone" Chem.Lett.97-98 (1998)
[Publications] Y.CHE: "Solvatochromic Linear Solvation Energy Relationships for Solubility of O_2 in Various Solvents" Bull.Chem.Soc.Jpn.71. 651-656 (1998)
[Publications] K.V.GOBI: "Electrochemical and Spectroscopic Studies on Nickel(II/III)Complexes with Novel 14-membered Hexaaza…" Electrochim.Acta. 43・9. 1013-1021 (1998)
[Publications] K.V.GOBI: "Electrochemical and Spectral Properties of Novel Dinickel(II)and Dicopper Complexes with N,N-linked…" Electrochim.Acta. 44. 269-278 (1998)
[Publications] K.V.GOBI: "Monolayer Films of a Nickel(II)Pentaazamacrocyclic Complex for the Electrocatalytic Oxidation of Hydrogen…" J.Electroanal.Chem.444. 145-150 (1998)
[Publications] K.V.GOBI: "Electrochemical Characteristics of Self-Assembled Monolayers of a Novel Nickei(II)Pentaazamacrocylic…" Langmuir. 14・5. 1108-1115 (1998)
[Publications] K.YAMADA: "Microelectrode with Leak of Solution" Denki Kagaku. 66・3. 321-325 (1998)
[Publications] F.KITAMURA: "In Situ IR Spectroscopic Study of Water at a Polycrystalline Gold Electrode Surface" J.Electroanal.Chem.452・1〜2. 241-249 (1998)
[Publications] F.KITAMURA: "Kinetic and In Situ Infrared Spectroscopic Study of Fe(W)_6^<3-/4-> Couple on a Platinum Single Crystal Electrode" J.Electroanal.Chem.456・1〜2. 113-120 (1998)
[Publications] S.KISHIOKA: "Spectroelectrochemical Detection of an Intermediate in the Alcohol Oxidation Process with a Nitroxyl Radical" Chem.Lett.343-344 (1998)
[Publications] S.KISHIOKA: "Reaction Mechanism and Kinetics of Alcohol Oxidation at Nitroxyl Radical Modified Electrodes" J.Electroanal.Chem.452・1〜2. 179-186 (1998)
[Publications] Y.B.LIAO: "Normal Pulse Voltammetry for Facilitated Ion Transfer Processes across Two Immiscible Liquid-Liquid…" Electrochim.Acta. 44. 117-124 (1998)
[Publications] 大坂武男: "O_3とO_2-オゾンがこわれるしくみ-" 化学と教育. 46・2. 100-104 (1998)
[Publications] K.V.GOBI: "Interfacial Infrared Reflection Spectroscopic Evidence for Potential-Dependent Electrocatalytic…" J.Phys.Chem.B. 103・1. 83-88 (1999)
[Publications] J.F.WU: "Hydrodynamic Chronocoulometric Determination of Diffusion coefficients and Concentrations of Dioxygen…" Anal.Chem.(発表予定). (1999)
[Publications] S.A.JOHN: "A Monomer-Dimer Equilibrium in Self-Assembled Monolayers of N-Ethyl-N'-Octadecylviologen…" J.Electroanal.Chem.(発表予定). (1999)
[Publications] K.V.GOBI: "Enhanced Electrostatic Interactions for Selective and Controllable Permeation of Ionic Species…" J.Electroanal.Chem.(発表予定). (1999)
[Publications] S.A.JOHN: "Electrocatalytic Reduction of Dioxygen by the Assembly of Asymmetric Viologen on Gold Electrodes" J.J.Deuterium Sci.(発表予定). (1999)
[Publications] K.V.GOBI: "Selective Anion Recognition and Electrochemical Characteristics of a Self-Assembled Monolayer of Nickel(II)…" J.Electroanal.Chem.(発表予定). (1999)
[Publications] 大坂武男(分担): "表面技術便覧" 日刊工業新聞社(表面技術協会編), 1386 (1998)
[Publications] 大坂武男(共著): "活性酸素とくらし(発表予定)" 丸善(株), (1999)

1998 Fiscal Year Annual Research Report

活性酸素種の生成・検出・反応制御に関する電気化学的アプローチ

Principal Investigator

大坂 武男 東京工業大学, 大学院・総合理工学研究科, 教授 (80152099)

Research Products

[Publications] Y.CHE: "New Oscillatory Phenomena in the Redox Reaction of O_2/O_2-Couple on Hanging Mercury Drop Electrode in Acetone" Chem.Lett.97-98 (1998)

[Publications] Y.CHE: "Solvatochromic Linear Solvation Energy Relationships for Solubility of O_2 in Various Solvents" Bull.Chem.Soc.Jpn.71. 651-656 (1998)

[Publications] K.V.GOBI: "Electrochemical and Spectroscopic Studies on Nickel(II/III)Complexes with Novel 14-membered Hexaaza…" Electrochim.Acta. 43・9. 1013-1021 (1998)

[Publications] K.V.GOBI: "Electrochemical and Spectral Properties of Novel Dinickel(II)and Dicopper Complexes with N,N-linked…" Electrochim.Acta. 44. 269-278 (1998)

[Publications] K.V.GOBI: "Monolayer Films of a Nickel(II)Pentaazamacrocyclic Complex for the Electrocatalytic Oxidation of Hydrogen…" J.Electroanal.Chem.444. 145-150 (1998)

[Publications] K.V.GOBI: "Electrochemical Characteristics of Self-Assembled Monolayers of a Novel Nickei(II)Pentaazamacrocylic…" Langmuir. 14・5. 1108-1115 (1998)

[Publications] K.YAMADA: "Microelectrode with Leak of Solution" Denki Kagaku. 66・3. 321-325 (1998)

[Publications] F.KITAMURA: "In Situ IR Spectroscopic Study of Water at a Polycrystalline Gold Electrode Surface" J.Electroanal.Chem.452・1〜2. 241-249 (1998)

[Publications] F.KITAMURA: "Kinetic and In Situ Infrared Spectroscopic Study of Fe(W)_6^<3-/4-> Couple on a Platinum Single Crystal Electrode" J.Electroanal.Chem.456・1〜2. 113-120 (1998)

[Publications] S.KISHIOKA: "Spectroelectrochemical Detection of an Intermediate in the Alcohol Oxidation Process with a Nitroxyl Radical" Chem.Lett.343-344 (1998)

[Publications] S.KISHIOKA: "Reaction Mechanism and Kinetics of Alcohol Oxidation at Nitroxyl Radical Modified Electrodes" J.Electroanal.Chem.452・1〜2. 179-186 (1998)

[Publications] Y.B.LIAO: "Normal Pulse Voltammetry for Facilitated Ion Transfer Processes across Two Immiscible Liquid-Liquid…" Electrochim.Acta. 44. 117-124 (1998)

[Publications] 大坂武男: "O_3とO_2-オゾンがこわれるしくみ-" 化学と教育. 46・2. 100-104 (1998)

[Publications] K.V.GOBI: "Interfacial Infrared Reflection Spectroscopic Evidence for Potential-Dependent Electrocatalytic…" J.Phys.Chem.B. 103・1. 83-88 (1999)

[Publications] J.F.WU: "Hydrodynamic Chronocoulometric Determination of Diffusion coefficients and Concentrations of Dioxygen…" Anal.Chem.(発表予定). (1999)

[Publications] S.A.JOHN: "A Monomer-Dimer Equilibrium in Self-Assembled Monolayers of N-Ethyl-N'-Octadecylviologen…" J.Electroanal.Chem.(発表予定). (1999)

[Publications] K.V.GOBI: "Enhanced Electrostatic Interactions for Selective and Controllable Permeation of Ionic Species…" J.Electroanal.Chem.(発表予定). (1999)

[Publications] S.A.JOHN: "Electrocatalytic Reduction of Dioxygen by the Assembly of Asymmetric Viologen on Gold Electrodes" J.J.Deuterium Sci.(発表予定). (1999)

[Publications] K.V.GOBI: "Selective Anion Recognition and Electrochemical Characteristics of a Self-Assembled Monolayer of Nickel(II)…" J.Electroanal.Chem.(発表予定). (1999)

[Publications] 大坂武男(分担): "表面技術便覧" 日刊工業新聞社(表面技術協会編), 1386 (1998)

[Publications] 大坂武男(共著): "活性酸素とくらし(発表予定)" 丸善(株), (1999)

大坂武男東京工業大学, 大学院・総合理工学研究科, 教授 (80152099)