電子移動反応場の設計と制御

1995 Fiscal Year Annual Research Report

• Project/Area Number: 05235103
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: 野中 勉 東京工業大学, 大学院・総合理工学研究科, 教授 (00016528)
• Co-Investigator(Kenkyū-buntansha): 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)
• Keywords: 電子移動 / 電極界面 / 電極修飾 / 電極反応

Research Abstract

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。

Research Products

• [Publications] Tsutomu NONAKA: "Kinetic Study of the Electroreduction of Benzoic Acid" Bull. Chem. Soc. Jpn.68. 378-384 (1995)
• [Publications] Naotake SATO: "Electrocatalytic Activity of Poly (tetrafluoroaniline)Film-Coated Electrodes for Fe3+12+Redox Response" Denki Kagaku. 63. 437-439 (1995)
• [Publications] Po-Chang CHEN: "Influences of Electrolytic Conditions on Emulsion Electrolysis: n-Octanol Oxidation" Denki Kagaku. 63. 395-399 (1995)
• [Publications] Mahito ATOBE: "U1trasonic Effects on Electroorganic Processes. Electroreduction of Benzaldehydes on Ultrasound-vibrating Electrodes" Chem. Lett.669-670 (1995)
• [Publications] Naotake SATO: "Electropolymerization of o-Mercaptoniline Monolayer Self assembled onan Au Electrode" Chem. Lett.805-806 (1995)
• [Publications] Katsuhiko TSUNASHIMA: "Product-Selectivity Control in an Electroorganic Process by Temperature. Electroreduction of Acetophenone" Chem. Lett.862-862 (1995)
• [Publications] Mahito ATOBE,: "Ultrasonic Effects on Electroorganic Processes. Part 4. Theoretical and Experimental Studies on Products-selectivity in Electroreduction of Benzaldehyde and Benzoic Acid" Electroanalysis.
• [Publications] 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)
• [Publications] 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)
• [Publications] 斉藤美佳子: "微小電極を用いた細胞電位の測定" DENKIKAGAKU. 64. 107-111 (1996)
• [Publications] Mikako Saito: "Application of Multifunctional Microelectrode to the in vivo Analysisof the K^+ Response to CO_2 Stress." Bioelectrochem. Bioenerg.(in press).
• [Publications] Ki-Bong Oh: "Rapid and Sensitive Screening of Antifungal Activity in Medicinal Plants by Single Cell Biosensing System." Biosci. Biotech. Biochem.(in press).
• [Publications] Ki-Bong Oh: "Transmission of the Effect of an Antifungal Agent within a Single Hypha." Appl. Microbiol. Biotechnol.(in press).
• [Publications] Kazuaki Yoshioka: "A Novel Fluorescent Derivative of Glucose Applicable to the Assessment of Glucose Uptake Activity of Escherichia coli." Biochem. Biophys. Acta. (in press).
• [Publications] Ki-Bong Oh: "Morphological Recognition of Fungal Spore Germination by a Computer-aided Image Analysis and Its Application to Antifungal Activity Evaluation." J. Biotechnology. (in press).
• [Publications] Jong-Chul Park: "Adaptation of Aspergillus nigerto Low pH Stress and Its Relation to Salt Stress and Miconazole." Mycological Research. (in press).
• [Publications] Hideaki Matsuoka: "Adaptation of Aspergillus niger to Multiple Agents Whose Action Mechanisms are Different" Jpn. J. Med. Mycol. 36. 19-24 (1995)
• [Publications] Hyeong-Cheol Yang: "Rapid Viability Assessment of Spores of Several Fungi by an Ionic Intensified Fluorescein Diacetate Method." Current Microbiol. 30. 173-176 (1995)
• [Publications] Hyeong-Cheol Yang: "Application of Microscopic Fluorescence Indicator to the Determination of Antimycotic Activity." J.Antibacterial Antifungal Agent. 23. 3-7 (1995)
• [Publications] Hideaki Matsuoka: "Use of Congo Red as a Microscopic Fluorescence Indicator of Hyphal Growth." Appl. Microbiol. Biotechnol.43. 102-108 (1995)
• [Publications] Ki-Bong Oh: "Combined Effect of Amphotericin B and Flucytosine on Hyphal Growth of Candida albicans Estimated at a SingleHypha Level." J. Med. Vet. Mycol.33. 191-195 (1995)
• [Publications] Mikako Saito: "Microinjection of Fluorescence Dye in a Plant Cell and Its Intercellular Translocation with a Multi-channelMicroelectrode System" Biochem. Biophys. Acta. (in press).
• [Publications] 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)
• [Publications] Y. Miyoshi, S. George, L. Okada,S. Miyazaki and M. Hirose: "In Situ Observation of Surface Reactions during Plasma Enhanced CVD using FT-IR-ATR" Proceeding of the 16th Symposium on Dry Process. 151-156 (1994)
• [Publications] 広瀬全孝・宮崎誠一: "高流動性プラズマCVDによる薄膜形成" 応用物理. 63. 1118-1122 (1994)
• [Publications] 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)
• [Publications] Y. Miyoshi, Y. Yoshida, S. Miyazaki and M. Hirose: "Real Time Observations of Surface Reactions during a-Si: H Deposition or H_2 Plasma Annealing by Using FT-IR-ATR" Abstracts of the 16th International Conference on Amorphous Semiconductors: Science and Technology. 183-183 (1995)
• [Publications] Y. Miyoshi, Y. Yoshida, S. Miyazaki and M. Hirose: "Real Time Observations of Surface Reactions during a-Si: H Deposition or H_2 Plasma Annealing by Using FT-IR-ATR" Journal of Non-Crystalline Solids. (掲載決定). (1996)
• [Publications] Yasuhiro Ogino: "Reactions between diaphorase andquincne compounds in bioelectrocatalytic redox reaction of NADH and NAD" J. Electroanal. Chem.396. 517-524 (1995)
• [Publications] Katsumi Takayama: "Bioelectrocatalytic Hydroxylation of nicotinic acid at on electrode madified with immckilized bacterial cells of P. fluorescens in the presence ofelectron trancfer mediators" J. Electroanal. Chem.381. 47-53 (1995)
• [Publications] Shinobu Itoh: "A Model Compound of Novel Cofactor Tryptophan Tryptopylquinone of Bacterial Methylamine Dehydrogenases. Synthesis and Physicochemical Preperties" J. Am. Chem.Soc.117. 1485-1493 (1995)
• [Publications] M. Tessema: "Flow injection amperometric determination of glucose and some other low molecular weight saccharides based on oligosacchaide dehydrogenase." Anal. Chim.Acta. 310. 161-171 (1995)
• [Publications] Kenji Kana: "Quinone-Mediated Bioelectrochemical Reduction of NAD(p)^+ Catalyzed by Flavoproteins" Chem. Lett.589-590 (1995)
• [Publications] Yukihiro Esaka: "Hydrogen-bonding interaction incapillary electrophoresis Using Solyether matrices" J. Chromatogr. A. 711. 305-311 (1995)
• [Publications] S. Yoshida, H. Kanno,T.Watanabe: "Glutamate Censors Canrrying Glutamate Oxidase/Peroxidase Bienzyme System on Tin Oxide Electrode" Analytical Sciences. 11. 251-256 (1995)
• [Publications] 鈴木一路,吉田寿一郎 渡辺正: "導電性ポリマーを用いるバイオセンサー" 生産研究. 47. 152-158 (1996)
• [Publications] 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)
• [Publications] 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)
• [Publications] H. Sakai and Fujishima etc.: "Local Detection of Photoelectrochemically Produced H202 with a “Wired"Horseradish Peroxidase Microsensor" The Joumal of Physical Chemistry. 99(31). 11896-11900 (1995)
• [Publications] H. Matsubara and Fujishima etc.: "Photoactive TiO2 Containing Paper : Preparation and Its Photocatalytic Activity under Weak UV Light Illumination" Chemistry Letters. 767-768 (1995)
• [Publications] T. Kawasaki and A. Fujishima etc.: "Imaging of One-Dimensional Conducting Pt Complexes Using Atomic ForceMicroscopy" Chemistry Letters. 879-880 (1995)
• [Publications] 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)
• [Publications] K. Ikeda and A. Fujishima etc.: "Microscopic Observation of Photocatalytic Reaction Using Microelectrode: Special Resolution for Reaction Products Distribution" Chemistry Letters. 979-980 (1995)
• [Publications] K. Ajito and A. Fujishima etc.: "Study of the Photochromic Properties of Amorphous MoO3 Films Using Raman Microscopy" The Joumal of Physical Chemistry. 99(44). 16383-16388 (1995)
• [Publications] T. Kato and A. Fujishima etc.: "Photoelectrochemical Reduction of Tetrazolium Salts to Formazans on Surfaces of Semiconductor Powders in Alcohol Solutions" Spectroscopy Letters.28(6). 849-859 (1995)
• [Publications] 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)
• [Publications] I. Sopyan and A. Fujishima etc.: "Efficient TiO2 Powder and Film Photocatalysts with Rutile Crystal Structure" Chemistry Letters. 69-70 (1996)
• [Publications] I. F. Zhi and A. Fujishima etc.: "Photoelectrochromic Properties of a Spirobenzopyran Derivative" Joumal of Photochemisry and Photobiology A: Chemistry. 92. 91-97 (1995)
• [Publications] R. Wang and A. Fujishima etc.: "Pola rized Photoelectrochemical Reaction of an Azobenzene Derivative in Langmuir-Blodgett Films" Joumal of Photochemisry and Photobiology A:Chemistry. 92. 111-116 (1995)
• [Publications] I. Mogi: "Control of the Dopant-Exchnage Process in Polypyrrole by a Magnetic Field" Chemistry Letters. 53-54 (1996)
• [Publications] I. Mogi and M. Kamiko: "Magnetic-Field-Induced Diffusion-Limited-Aggregation in Electrodeposition" J. Phys. Soc. Jpn.64. 4500-4503 (1995)
• [Publications] I. Mogi and M. Kamiko and S. Okubo: "Magnetic Field Effects on Fractal Morphology in Electrochemical Deposition" Physica B. 211. 319-322 (1995)
• [Publications] I. Mogi: "Electrochemical Studies in Steady High Magnetic Fields" Physica B. (in press). (1996)
• [Publications] I. Mogi and M. Kamiko: "Striking Effects of Magnetic Field on the Growth Morphology of Electrochemical Deposits" J. Crystal Growth. (in press). (1996)
• [Publications] I. Mogi: "Novel Electrochemical Phenomenain Magnetic Fields" Sci. Rep. RITU. (in press). (1996)
• [Publications] Tokuji Ikeda: "Frontiers of Biosensorics ed. F. Scheller(分担)" Birkhauser(印刷中), (1996)
• [Publications] 池田篤治: "分析化学(酵素機能電極の研究)" 333-354 (1995)
• [Publications] 渡辺正,中林誠一郎: "電子移動の化学-電気化学入門" 朝倉書店, 200 (1996)