1999 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 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 / スーパーオキシドイオン / 酸素 / 過酸化水素 / 酵素 / 電気化学振動現象 / 電極触媒 / 自己組織化単分子膜
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^-,過酸化水素水H_2O_2,ヒドロペルオキシラジカルHO_2・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.新規大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,H_2O_2のO_2への電極触媒酸化における触媒能の電位依存性及び電解質アニオン依存性をin situ FTIR分光法を用いて解明し,特異な触媒反応のメカニズムを提案した。 2.ガス拡散電極を様々な有機化合物で修飾した分子修飾電極を構築し,O_2の電解還元によるH_2O_2生成に対して,高電流密度電解での高い生成効率の実現に成功した。 3.アルキルビオロゲンSAM電極を構築し,O_2のH_2O_2への著しい電極触媒還元能を見い出した。 4.一連のキノリン溶媒中で,O_2^-レドックス対の電極反応を定量的に解析し,またO_2^-によって誘起される特異な電気化学振動現象をはじめて見い出し,そのメカニズムを提案した。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] S.A.JOHN: "Electrochemical and EQCM Studies on the Assembly of Asymetric Viologen on Bare and Alkanethiol-Coated Au Electrldes"J. Electroanal. Chem.. 477. 52-61 (1999)
[Publications] K.ARIHARA: "Voltammetric and Spectroscopic Study of the Adsorption of Alkyl Viologens on a HOPG Electrode"J. Electroanal. Chem.. 473. 138-144 (1999)
[Publications] T.OKAJIMA: "Electrochemical Behavior of a Cypridina Luciferin Analogue in Acetonitrile Solutions - - -"J. Electroanal. Chem.. 476. 46-53 (1999)
[Publications] J.F.WU: "Hydrodynamic Chronocoulometric Determination of Diffusion Coefficients and Concentrations of Dioxygen in Media - - -"Anal. Chem.. 71. 4056-4060 (1999)
[Publications] J.F.WU: "Electroreduction of Oxygen in Quinoline and Isoquinoline"Electrochim. Acta. 45. 987-991 (1999)
[Publications] K.V.GOBI: "Enhanced Electrostatic Interactions for Selective and Controllable Permeation of Ionic Species at - - -"J. Electroanal. Chem.. 465. 177-186 (1999)
[Publications] K.V.GOBI: "Interfacial Infrared Reflection Spectroscopic Evidence for Potential-Dependent Electrocatalytic Activity ---"J. Phys. Chem. B. 103. 83-88 (1999)
[Publications] S.A.JOHN: "Use of Alkanethiol-Coated Electrodes to Study the Importance of Water Content on the Electrochemical---"Langmuir. 15. 3816-3822 (1999)
[Publications] S.A.JOHN: "A Monomer-Dimer Equilibrium in Self-Assembled Monolayers of N-Ethyl-N'-Octadecyl, Viologen---"J. Electroanal. Chem.. 466. 67-74 (1999)
[Publications] C.HARNOODE: "Electrochemical and Spectroelectrochemical Studies on Sandwich-type Bis (phthalocyaminato) Lanthanide ---"Electrochemistry. 67. 832-838 (1999)
[Publications] S.A.JOHN: "Electrocatalytic Reduction of Dioxygen by the Assembly of Asymmetric Viologen on Gold Electrodes---"Jpn. J. Deuterium Sci.. 8. 17-23 (1999)
[Publications] N.NANBU: "Adsorption of Pyridine on a Polycrystalline Gold Electrode Sueface Studied by Infrared Reflection"J. Electroanal. Chem.. 470. 136-143 (1999)
[Publications] C.R.RAJ: "Simultaneous Detection of Ascorbic Acid and Dopoamine at Gold Electrode Modified with a self ---"Electrochemistry. 67. 1175-1777 (1999)
[Publications] N.WAKABAYASHI: "Effect of Aions on the Kinetics of Tris (1,10-phenane-Ahroline) cobalt (II)/(III) Redox-Electrode Reaction ---"Electrochemistry. 67. 1181-1183 (1999)
[Publications] N.NANBU: "Adsorption Behavior of Pyridinecarboxylic Acids in Acidic solution on a Dolycrystalline Gold Electrode ---"Electrochemistry. 67. 1165-1167 (1999)
[Publications] S.A.JOHN: "Stabilization of the Assemblies of Short Alkyl Chain Asymmetric Viologens on Alkanethiol-Coated Electrodes ---"Electrochim. Acta. 45. 1127-1133 (1999)
[Publications] S.A.JOHN: "Alkanethiol Structure and Supporting Electrolyte Effects on the Electrochemical and in situ Fourier Transform IR ---"Langmuir. 16(in pres). (2000)
[Publications] C.R.RAJ: "Electrocatalytic Oxidation of NADH at the Self-Assembled Monolayer of Nickel (II) Macrocyle ---"Bioelectrochem.Bioenerg.. 45(in press). (2000)
[Publications] 北村房男: "電極/溶液界面の分子組織化:界面分子・イオンのダイナミック挙動"表面. 37. 661-677 (1999)
[Publications] 大坂武男: "活性酸素"丸善(株). 136 (1999)
[Publications] 大坂武男: "電気化学便覧第5版"丸善(株) (発表予定). (2000)

1999 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] S.A.JOHN: "Electrochemical and EQCM Studies on the Assembly of Asymetric Viologen on Bare and Alkanethiol-Coated Au Electrldes"J. Electroanal. Chem.. 477. 52-61 (1999)

[Publications] K.ARIHARA: "Voltammetric and Spectroscopic Study of the Adsorption of Alkyl Viologens on a HOPG Electrode"J. Electroanal. Chem.. 473. 138-144 (1999)

[Publications] T.OKAJIMA: "Electrochemical Behavior of a Cypridina Luciferin Analogue in Acetonitrile Solutions - - -"J. Electroanal. Chem.. 476. 46-53 (1999)

[Publications] J.F.WU: "Hydrodynamic Chronocoulometric Determination of Diffusion Coefficients and Concentrations of Dioxygen in Media - - -"Anal. Chem.. 71. 4056-4060 (1999)

[Publications] J.F.WU: "Electroreduction of Oxygen in Quinoline and Isoquinoline"Electrochim. Acta. 45. 987-991 (1999)

[Publications] K.V.GOBI: "Enhanced Electrostatic Interactions for Selective and Controllable Permeation of Ionic Species at - - -"J. Electroanal. Chem.. 465. 177-186 (1999)

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

[Publications] S.A.JOHN: "Use of Alkanethiol-Coated Electrodes to Study the Importance of Water Content on the Electrochemical---"Langmuir. 15. 3816-3822 (1999)

[Publications] S.A.JOHN: "A Monomer-Dimer Equilibrium in Self-Assembled Monolayers of N-Ethyl-N'-Octadecyl, Viologen---"J. Electroanal. Chem.. 466. 67-74 (1999)

[Publications] C.HARNOODE: "Electrochemical and Spectroelectrochemical Studies on Sandwich-type Bis (phthalocyaminato) Lanthanide ---"Electrochemistry. 67. 832-838 (1999)

[Publications] S.A.JOHN: "Electrocatalytic Reduction of Dioxygen by the Assembly of Asymmetric Viologen on Gold Electrodes---"Jpn. J. Deuterium Sci.. 8. 17-23 (1999)

[Publications] N.NANBU: "Adsorption of Pyridine on a Polycrystalline Gold Electrode Sueface Studied by Infrared Reflection"J. Electroanal. Chem.. 470. 136-143 (1999)

[Publications] C.R.RAJ: "Simultaneous Detection of Ascorbic Acid and Dopoamine at Gold Electrode Modified with a self ---"Electrochemistry. 67. 1175-1777 (1999)

[Publications] N.WAKABAYASHI: "Effect of Aions on the Kinetics of Tris (1,10-phenane-Ahroline) cobalt (II)/(III) Redox-Electrode Reaction ---"Electrochemistry. 67. 1181-1183 (1999)

[Publications] N.NANBU: "Adsorption Behavior of Pyridinecarboxylic Acids in Acidic solution on a Dolycrystalline Gold Electrode ---"Electrochemistry. 67. 1165-1167 (1999)

[Publications] S.A.JOHN: "Stabilization of the Assemblies of Short Alkyl Chain Asymmetric Viologens on Alkanethiol-Coated Electrodes ---"Electrochim. Acta. 45. 1127-1133 (1999)

[Publications] S.A.JOHN: "Alkanethiol Structure and Supporting Electrolyte Effects on the Electrochemical and in situ Fourier Transform IR ---"Langmuir. 16(in pres). (2000)

[Publications] C.R.RAJ: "Electrocatalytic Oxidation of NADH at the Self-Assembled Monolayer of Nickel (II) Macrocyle ---"Bioelectrochem.Bioenerg.. 45(in press). (2000)

[Publications] 北村房男: "電極/溶液界面の分子組織化:界面分子・イオンのダイナミック挙動"表面. 37. 661-677 (1999)

[Publications] 大坂武男: "活性酸素"丸善(株). 136 (1999)

[Publications] 大坂武男: "電気化学便覧第5版"丸善(株) (発表予定). (2000)

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