電子移動反応場の設計と制御

1995 年度 実績報告書

• 研究課題/領域番号: 05235103
• 研究機関: 東京工業大学
• 研究代表者: 野中 勉 東京工業大学, 大学院・総合理工学研究科, 教授 (00016528)
• 研究分担者: 渡辺 正 東京大学, 生産技術研究所, 教授 (70092385) ; 茂木 巌 東北大学, 金属材料研究所, 助手 (50210084) ; 松岡 英明 東京農工大学, 工学部, 教授 (10143653) ; 藤嶋 昭 東京大学, 工学部, 教授 (30078307) ; 池田 篤治 京都大学, 農学部, 教授 (40026422)
• キーワード: 電子移動 / 電極界面 / 電極修飾 / 電極反応

研究概要

本研究課題である「電子移動反応場の設計と制御」は、電極表面のみならず、電極界面全体に及ぶ新しい電極修飾の概念、原理および手法の確立によって初めて達成されうるとの基本理念が、以下に述べる研究成果に基づいて検証された。すなわち、電極修飾の新しい概念は下記の4つの大別され、その各々が独立して、また相互に連携して、次世代の有機電気化学の展開を主導するものであり、その骨子とするところは有機電極反応の帰納的、能動的かつ合目的的な超精密制御にあると結論された。以下の記述は計画班員による成果と,今年度は公募班員による貢献も大きく,これも加えて成果の要点を述べる。
(1)電極界面の物資修飾のよる反応場の設計と制御
レドックス対、分子識別物資、不斉誘導物資、親/疎水性物資、光感応物資、触媒、酵素、生体系物資などの広範な機能性物資で修飾した電極が設計・作製され、それらの高度な機能を活用した高効率あるいは新規な分子変換の実現が大巾に拡充された。さらに,電解酸化重合法による高分子単分子膜形成の可能性が検証され,超分子機能への新しい展開が期待されることとなった。また,電気化学的異方性をもつ電極の設計と機能が急速に進んだ。
(2)電極界面の形態/状態修飾による反応場の設計と制御
電極表面の超高表面積化、巨視的不均一化、浸透性化など、並びに電解液界面の気相化、固相化、超流動化などによる新しいタイプの有機電気化学分子変換が創成され、従来の古典的な電解質溶液論や電気二重層概念を超越した理論の展開をみた。とくに、気相電解法の開拓研究は一層進み、実用的展開を指呼するところまで達した。
(3)電解液界面のエネルギー照射修飾による反応場の設計し制御
電解液界面のエネルギー照射修飾による反応場の設計と制御
電導体電極系の電解液界面にプラズマ,光,磁場,超音波などの物理的エネルギーを照射することにより、電気化学的エネルギーだけでは不可能な新しい多様な有機電極反応が実現された。とくに、磁場と力学場の多重印加による著しい効果に関する研究が急伸し、新しい化学への展開が予見されることなった。
(4)超微小電極界面反応場の設計と制御
公募研究により着手され、炭素繊維電極について成果が蓄積されつつある。しかし、理論的側面に若干の不十分を残している。

研究成果

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• [文献書誌] Naotake SATO: "Electropolymerization of o-Mercaptoniline Monolayer Self assembled onan Au Electrode" Chem. Lett.805-806 (1995)
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• [文献書誌] Mahito ATOBE,: "Ultrasonic Effects on Electroorganic Processes. Part 4. Theoretical and Experimental Studies on Products-selectivity in Electroreduction of Benzaldehyde and Benzoic Acid" Electroanalysis.
• [文献書誌] 松岡英明: "バイオセンシング技術の展望" 防菌防黴雑誌. 23. 487-494 (1995)
• [文献書誌] 松岡英明: "植物生葉の環境センサー機能の開発" 日本化学会誌. 415-425 (1995)
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• [文献書誌] Mikako Saito: "Microinjection of Fluorescence Dye in a Plant Cell and Its Intercellular Translocation with a Multi-channelMicroelectrode System" Biochem. Biophys. Acta. (in press).
• [文献書誌] S. Miyazaki, H. Shin, Y. Miyoshi and M. Hirose: "Real Time Monitoring of SurfaceReactions during Plasma Enhanced CVD ofSilicon" Extended Abstracts of the 1994 International Conference on Solid State Devices and Materials. 724-726 (1994)
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• [文献書誌] S. Miyazaki, H. Shin, Y. Miyoshi and M. Hirose: "Real Time Monitoring of SurfaceReactions during Plasma Enhanced CVD ofSilicon" Japanese Journal of Applied Physics. 34. 787-790 (1995)
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• [文献書誌] Yasuhiro Ogino: "Reactions between diaphorase andquincne compounds in bioelectrocatalytic redox reaction of NADH and NAD" J. Electroanal. Chem.396. 517-524 (1995)
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• [文献書誌] R. Wang and A. Fujishima etc.: "Selective In-Plane Photoelectrochemical Reaction of an Azobenzene Derivative in an Assembled Film" The Joumal of Physical Chemistry. 99(10). 3352-3356 (1995)
• [文献書誌] T.Nakashima and A.Fujishima etc.: "Adsorption of Anionic and Cationic Dyes in Dilute Solutions onto a SnO2 Surface Measured by Total Intemal Reflection Fluorescence" Ber. Bunsenges. Phys. Chem.99(4). 609-616 (1995)
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• [文献書誌] K.Morigaki and A. Fujishima etc.: "Azobenzene-Derivative Langmuir-Blodgett Films Deposited on Various Thiol Monolayers" The Joumal of Physical Chemistry. 99(40). 14771-14777 (1995)
• [文献書誌] K. Ikeda and A. Fujishima etc.: "Microscopic Observation of Photocatalytic Reaction Using Microelectrode: Special Resolution for Reaction Products Distribution" Chemistry Letters. 979-980 (1995)
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• [文献書誌] K. Hashimoto and A. Fujishima etc.: "Structural Analysis of a DiamondFilm Grown on a Photoelectrochemically Etched Silicon Substrate by Micro-Raman Spectroscopy" J. Electroanal. Chem.397. 339-341 (1995)
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