1997 Fiscal Year Annual Research Report

特異反応場を有する界面ナノ組織体の構築

Research Project

Project/Area Number	09232221
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, 助教授 (80152099)
Keywords	酵素電極 / 自己組織化膜 / ナノ組織体 / スーパーオキシドイオン / 電子移動反応 / 過酸化水素 / 電解 / チオール化合物
Research Abstract	本研究では、活性酸素種の生成,反応制御及び検出のための電極システムの構築に,自己組織化単分子層(self-assembled monolayer, SAM)を用いる電極界面のナノ組織化を展開し,さらにその電子移動及び触媒機能を制御することを目的として行われ,本年度は次の成果を得た。 1.新規環状金属錯体として14員環のペンタアザ環状ニッケル及び銅ニ重体のテンプレート合成法を確立し,さらにAu-S結合を利用して金属電極表面上にこの環状錯体が自己組織化した単分子層(SAM)修飾電極を構築した。これらのSAM電極はH_2O_2の0_2への著しい電極酸化触媒能を有し,その触媒酸化電位を電解質アニオンの選択によって制御できることを見い出し,そのメカニをin situ FTIR分光法で解明した。 2.チオフェノール誘導体を電極表面に自己組織化した電極を用いることによって,水溶液系でスーパーオキシドイオンを電解生成できることをはじめて見い出し,その確証実験を行った。 3.非対称アルキルビオロゲンのSAMを一電子電解還元すると,単分子層内でビオロゲンの2量化,さらには界面モノマー/ダイマーの平衡が起こることを明らかにし,またO_2のH_2O_2への還元を著しく電極触媒することを見い出した。

Research Products
(15 results)

All Other

All Publications (15 results)

[Publications] Yong CHE: "Solvatochromic Linear Solvation Energy Relationship for Solubility of O_2 in Various Media Containing Tetraethylammonium Perchlorate" Anal. Sci.13. 1039-1042 (1997)
[Publications] K.V.GOBI: "Voltammetric Behavior of Self-Assembled Monolayers of Novel Nickel (II/III) Pentaazamacrocyclic Complex on Gold Electrode" Denki Kagaku. 65. 498-500 (1997)
[Publications] Fusao KITAMURA: "Infrared Spectroscopic Observation of Water at a Gold Electrode/Aqueous Perchlorate Solution Interface" Electrochim. Acta. 42. 1235-1238 (1997)
[Publications] M.K.OH: "Electrocatalytic Reduction of Dioxygen in the Presence of N, N′-Dipentyl Viologen" Chem. Lett.1997. 67-68 (1997)
[Publications] S.A.JOHN: "Electrochmical Study on Monomer/Dimer Equilibria of a Series of Asymmetric Viologen Monolayers on Electrode Surface" J. Electroanal. Chem.436. 267-270 (1997)
[Publications] Yong CHE: "New Oscillatory Phenomena in the Redox Reaction of O_2/O^-_2 Couple on a Hanging Mercury Drop Electrode in Acetone Media" Chem. Lett.1998. 97-98 (1998)
[Publications] K.V.GOBI: "Electrochmical Characterisrics of Self-Assembled Monolayers of Novel Nickel (II) Pentaazamacrocyclic Complex on Gold Electrode" Langmuir. 14(発表予定). (1998)
[Publications] K.V.GOBI: "Monomolecular Films of Nickel (II) Pentaazamacrocyclic Complex for Electrocatalylic Oxidation of Hydrogen Peroxide at Gold Electrodes" J. Electroanal. Chem.(発表予定). (1998)
[Publications] Shinya KISHIOKA: "Reaction Mechanism and Kinetics of Alcohol Oxidation at Nitroxyl Radical Modified Electrodes" J. Electroanal. Chem.(発表予定). (1998)
[Publications] Shinya KISHIOKA: "Spectroelectrochemical Detection of an Intermediate in the Alcohl Oxidation Process with a Nitroxyl Radical" Chem. Lett.1998(発表予定). (1998)
[Publications] K.V.GOBI: "Electrochemical and Spectroscopic Studies of Nickel (II/III) Complexes with Novel 14-Membered Hexaaza Macrocycle" Electrochim. Acta. (発表予定). (1998)
[Publications] Yong CHE: "Solvatochromic Linear Solvation Energy Relationships for Solubility of O_2 in Various Solvents" Bull. Chem. Soc. Jpn.71,No.3(発表予定). (1998)
[Publications] Keizo YAMADA: "Microelectrodes with Leak of Solution" Denki Kagaku. 66(発表予定). (1998)
[Publications] 大坂武男: "O_2 と O_3ーオゾンがこわれるしくみー" 化学と教育. 46(発表予定). (1998)
[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)(発表予定), (1998)

1997 Fiscal Year Annual Research Report

特異反応場を有する界面ナノ組織体の構築

Principal Investigator

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

Research Products

[Publications] Yong CHE: "Solvatochromic Linear Solvation Energy Relationship for Solubility of O_2 in Various Media Containing Tetraethylammonium Perchlorate" Anal. Sci.13. 1039-1042 (1997)

[Publications] K.V.GOBI: "Voltammetric Behavior of Self-Assembled Monolayers of Novel Nickel (II/III) Pentaazamacrocyclic Complex on Gold Electrode" Denki Kagaku. 65. 498-500 (1997)

[Publications] Fusao KITAMURA: "Infrared Spectroscopic Observation of Water at a Gold Electrode/Aqueous Perchlorate Solution Interface" Electrochim. Acta. 42. 1235-1238 (1997)

[Publications] M.K.OH: "Electrocatalytic Reduction of Dioxygen in the Presence of N, N′-Dipentyl Viologen" Chem. Lett.1997. 67-68 (1997)

[Publications] S.A.JOHN: "Electrochmical Study on Monomer/Dimer Equilibria of a Series of Asymmetric Viologen Monolayers on Electrode Surface" J. Electroanal. Chem.436. 267-270 (1997)

[Publications] Yong CHE: "New Oscillatory Phenomena in the Redox Reaction of O_2/O^-_2 Couple on a Hanging Mercury Drop Electrode in Acetone Media" Chem. Lett.1998. 97-98 (1998)

[Publications] K.V.GOBI: "Electrochmical Characterisrics of Self-Assembled Monolayers of Novel Nickel (II) Pentaazamacrocyclic Complex on Gold Electrode" Langmuir. 14(発表予定). (1998)

[Publications] K.V.GOBI: "Monomolecular Films of Nickel (II) Pentaazamacrocyclic Complex for Electrocatalylic Oxidation of Hydrogen Peroxide at Gold Electrodes" J. Electroanal. Chem.(発表予定). (1998)

[Publications] Shinya KISHIOKA: "Reaction Mechanism and Kinetics of Alcohol Oxidation at Nitroxyl Radical Modified Electrodes" J. Electroanal. Chem.(発表予定). (1998)

[Publications] Shinya KISHIOKA: "Spectroelectrochemical Detection of an Intermediate in the Alcohl Oxidation Process with a Nitroxyl Radical" Chem. Lett.1998(発表予定). (1998)

[Publications] K.V.GOBI: "Electrochemical and Spectroscopic Studies of Nickel (II/III) Complexes with Novel 14-Membered Hexaaza Macrocycle" Electrochim. Acta. (発表予定). (1998)

[Publications] Yong CHE: "Solvatochromic Linear Solvation Energy Relationships for Solubility of O_2 in Various Solvents" Bull. Chem. Soc. Jpn.71,No.3(発表予定). (1998)

[Publications] Keizo YAMADA: "Microelectrodes with Leak of Solution" Denki Kagaku. 66(発表予定). (1998)

[Publications] 大坂武男: "O_2 と O_3ーオゾンがこわれるしくみー" 化学と教育. 46(発表予定). (1998)

[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)(発表予定), (1998)

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