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1995 Fiscal Year Final Research Report Summary

Study on Electron Transfer Reaction of Superoxide Ion and Its In Vivo Detection

Research Project

Project/Area Number 05453117
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 工業物理化学
Research InstitutionTokyo Institute of Technology

Principal Investigator

OHSAKA Takeo  Tokyo Institute of Technology, Department of Electronic Chemistry, Associate Professor, 大学院・総合理工学研究科, 助教授 (80152099)

Co-Investigator(Kenkyū-buntansha) KITAMURA Fusao  Tokyo Institute of Technology, Department of Electronic Chemistry, Assistant Pro, 大学院・総合理工学研究科, 助手 (00224973)
OKAJIMA Takeyoshi  Tokyo Institute of Technology, Department of Electronic Chemistry, Assistant Pro, 大学院・総合理工学研究科, 助手 (70194347)
TOKUDA Koichi  Tokyo Institute of Technology, Department of Electronic Chemistry, Professor, 大学院・総合理工学研究科, 教授 (40016548)
Project Period (FY) 1993 – 1995
KeywordsSuperoxide Ion / Oxygen / Reactive Oxygen Species / Electron Transfer Reaction / Superoxide Dismutase / Molecularly Modified Electrodes / Electrolysis / Spectroelectro chemistry
Research Abstract

This research was conducted to fabricate model biological interfaces for elucidating biological electron transfer reactons as well as developing in vivo electrochemical sensor of superoxide ion (O_2^-). The following remarkable results were obtained.
1. Based on the self-assembling of surface-active molecules such as quinoline and thiophenol derivatives at electrode surfaces, the moleculary modified electrode systems have been developed to electrogenerate O_2^- by one-electron reduction of O_2 in aqueous media. A rigorous charge-time relationship for hydrodynamic chronocoulometry was derived and successfully applied to simutaneous determination of diffusion coefficients and concentrations of O_2 and O_2^- in various media.
2. The water-induced dismutation of the electrogenerated O_2^- ion in AN,DMF and DMSO containing various concentrations of water as Brphinsted acid has been examined by UV-vis spectroscopy and pulse electrolysis stopped-flow spectroscopy. The electrogenerated O_2^- ion was found to specifically react with Cypridin a Luciferin analogue to result ina characteristic chemiluminescence.
3. Methyl viologen and quinones were found to efficiently mediate the electron transfer between SOD and the electrode in DMSO media. We have for the first time observed the electrochemically well-behaved and stable redox response of SOD at cysteine-modified gold electrode in neutral aquous solution.

  • Research Products

    (58 results)

All Other

All Publications (58 results)

  • [Publications] Takeyoshi OKAJIMA: "Electrical Equivalent Circuit Parameters for Montmorillonite Clay Film-Coated Ouartz Crystals in Contact with Air,H_2O and Electrolyte Solutions" Electrochim. Acta. 38. 747-756 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takeo OHSAKA: "Reaction Entropies for the O_2/O_2^- Redox Couple in Aprotic Solvents" Bioelectrochem.& Bioenerg.31. 289-300 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takeo OHSAKA: "Electrocatalysis of Poly (thionine) -Modified Electrodes for Oxidation of Reduced Nicotinamide Adenine Dixucleotide" J.Chem.Soc.Chem.Commun.222-224 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Fusao KITAMURA: "Adsorption Behavior of Violoyen Derivatives on Hanging Merwry Electrode Surfaces" J.Electroanal.Chem.347. 371-381 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Noboru OYAMA: "Piezoelectric Admittance-Based Sensing of Electrolyte Solutions by Montmorillonite Clay Film-Coated Quartz Crystal Uscillators" Sensors and Actuators B. 13-14. 372-375 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Fusao KITAMURA: "In Situ Infrared Absorption Spectra of Heptyl Viologen Adsorbed on a Merwry Electrode Surfaces" J.Electroanal.Chem.353. 323-328 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takeo OHSAKA: "One-and Two-Electron Reduction of Molecular Uxygen Based on Electrode Surface Modification in Alkaline Aqueous Media" Denki Kagaku. 61. 763-766 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] C.Harnoode: "The Third Oxidation Potentials and the Third Reduction Potentials of Bis (phthalocyaninato) Lanthanide Complexes" Denki Kagaku. 61. 767-769 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Koichiro TANAKA: "An Excellent Electrocatalysis of Poly (phenosafranine) -modified Electrode for oxidation of Reduced β-Nicotinamide Adenine Dinucleetide" J.Chem.Soc.Chem.Commun.1770-1772 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Koichiro TANAKA: "Preparation of Poly (thionine) -modified Electrode and Its Application to an Electrochemical Detector for the Flow-Injection Analysis of NADH" Anal.Sci.9. 783-789 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 徳田耕一: "基礎電気化学測定法の新しい展開-回転リングデイスク電極-" 電気化学. 61. 193-197 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大坂武男: "酸素・活性酸素種の電子化学-アセトニトリル中で電解生成したスーパーオキシドイオンの不均化反応に関する分光学的研究-" J.Deuterium Sci.3. 47-54 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松本 太: "H_2O及びD_2O中でのスーパーオキシドイオンのジスムテーション" J.Deuterium Sci.3. 95-100 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大坂武男: "電気分解で金属やポリマーをつくる" 現代化学. 51-55 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大坂武男: "水溶液中でのスーパーオキシドイオンの電解生成" J.Deuterium Sci.4. 44-47 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takeo OHSAKA: "Diffusion Coefficients of Superoxide Ion in Vavious Media" Denki Kagaku. 62. 1300-1303 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hideharu SATOH: "A Study on Diffusional Behavior of Propyl Violoyen in Poly (ethylene Oxide) Polymer Solvents Based on a Comlined Use of Steady-state Cyclic Voltammetry and Patential-Stop Chronoamperometry" Electrochim.Acta. 39. 2261-2270 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.-T.XU: "Simultaneous Determination of Dopamine and Ascorbic Acid with Poly (3-methylthiophene) /Polypyrrole Bilayer-Coated Carbon Fiber Electrodes" Anal.Sci.10. 399-404 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] C.-W.LEE: "In Situ Electrochemical Quartz Crystal Microbalance Studies of Self-Assembled N-Docosyl-N′-Methyl Viologen Films at Gold Electrodes" Bull. Korean Chem.Soc.15. 190-191 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Fusao KITAMURA: "Effect of Complexation by Cyclodextrins on the Voltammetric Characteristic of Violoyens Adsorbed on an HMDE" J.Electronal. Chem.368. 281-284 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Fusao KITAMURA: "FT-IRAS Study of p-Cyanobenzoate Adsorption on a Polycrystalline Gold Electrode" Denki Kagaku. 62. 532-533 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Manabu TSUSHIMA: "Use of Hydrodynamic Chronocoulometry for Simultaneous Determination of Diffusion Coefficients and concentrations of Dioxygen in Various Media" Anal.Chem.66. 4551-4556 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takeo OHSAKA: "Midiated Electron-Transfer of Poly (ethylene) Dxide-Modified Superoxide Dismutase by Methyl Viologen" Bioelectrochem.& Bioenerg.37. 73-76 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Futoshi MATSUMOTO: "Electrogeneration of Superoxide Ion on Thiophenol-Midified Gold Electrode in Aqueous Solution" Denki Kagaku. 63. 1205-1208 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Koichi TOKUDA: "AC Voltammetry at Microcylinder Electrodes" J.Electroanal. Chem.396. 365-370 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Noboru OYAMA: "Coupling between Electron and Mass Transfer Kinetics in Electroactive Polymer Films. An Application of in Situ Quartz Crystal Electrode (QcE)" Prog.in Polym.Sci.20. 761-818 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hideharu SATOH: "Observation of Intermolecular Charge-Transfer Spectra for Propyl Violoyen Dihalides in a Series of Polyether Media" Chem.Lett.51-52 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Futoshi MATSUMOTO: "Electrogeneration of Superoxide Ion at Mercury Electrodes with a Hydrophobic Adsorption Film in Aqueous Media" Electroanalysis. (発表予定). (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Futoshi MATSUMOTO: "Electrogeneration of Superoxide Ion at α-Quinoline-Adsorbed Merwry Electrode in Alkaline Aqueous Solution" J.Deuterium Sci.(発表予定). (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Okajima: "Electrical Equivalent Circuit Parameters for Montmorillonite Clay Film-Coated Quartz Crystals in Contact with Air, H_2O and Electrolyte Solutions" Electrochim Acta. 38, [6]. 747-756 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "Reaction Entropies for the O_2/O_2^- Redox Couple in Aprotic solvents" Bioelectrochem.& Bioenerg.31. 289-300 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "Electrocatalysis of Poly (thionine)-Modified Electrodes for Oxidation of Reduced Nicotinamide Adenine Dinucleotide" J.Chem.Soc.Chem.Commun. [3]. 222-224 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Kitamura: "Adsorption Behavior of Viologen Derivatives on Hanging Mercury Electrode Surfaces" J.Electroanal.Chem.347. 371-381 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Oyama: "Piezoelectric Admittance-Based Sensing of Electrolyte Solutions by Montmorillonite Clay Film-coated Quartz Crystal Oscillators" Sensors and Actuators B. 13-14. 372-375 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Kitamura: "In Situ Infrared Absorption Spectra of Heptyl Viologen Adsorbed on a Mercury Electrode Surface" J.Electroanal.Chem.353 (1+2). 323-328 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "One-and Two-Electron Reduction of Molecular oxygen Based on Electrode Surface Modification in Alkaline Aqueous Media" J.Electrochem.Soc.Jpn.(Denki Kagaku). 61, [7]. 763-766 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] C.Harnoode: "The Third Oxidation Potentials and the Third Reduction Potentials of Bis (phthal-ocyaninato) Lanthanide Complexes" J.Electrochem.Soc., Jpn.(Denki Kagaku). 61, [7]. 767-769 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tanaka: "An Excellent Electrocatalysis of Poly (phenosafranine) -modified Electrode for Oxidation of Reduced beta-Nicotinamide Adenien Dinucleotide" J.Chem.Soc.Chem.Commun.[23]. 1770-1772 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tanaka: "Preparation of Poly (thionene)-modified Electrode and Its Application to an Electrochemical Detector for the Flow-Injection Analysis of NADH" Anal.Sci.9, [12]. 783-789 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tokuda: "New Trends in Foundamental Electrochemical Methods-Rotating Ring Disk Electrode" J.Electrochem.Soc.Jpn.(Denki Kagaku). 61. 193-197 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "Electronic Chemistry of Oxygen and Reactive Oxygen Species-Spectroscopic Study on Dismutation of Superoxide Ion Electrogenerated in Acetonitrile" J.Deuterium Sci.3. 47-54 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Matsumoto: "Dismutation of Superoxide Ion in H_2O and D_2O" J.Deuterium Sci.3. 95-100 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "Preparation of Metal and Polymer by Electrolysis" Gendai Kagaku. 51-55 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "Electrogeneration of Superoxide Ion in Aqueous Media" J.Deuterium Sci.4. 44-47 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "Diffusion Coefficients of Superoxide Ion in Various Media" J.Electrochem.Soc.Jpn.(Denki Kagaku). 62. 1300-1303 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Satoh: "A Study on Diffusional Behavior of Propyl Viologen in Poly (ethylene oxide) Polymer Solvents Based on a Combined use of Steady-state Cyclic Voltammetry and Potentialstep Chronoamperometry" Electrochem.Acta. 39. 2261-2270 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.-T.Xu: "Simultaneous Determination of Dopamine and Ascorbic Acid with Poly (3-methylthio-phene)/Plypyrroloe Bilayr-coated Carbon Fiber Electrodes" Anal.Sci.10. 399-404 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] C.-W.Lee: "In Situ Electrochemical Quartz Crystal Microbalance Studies of Self-Assembled N-Docosyl-N'-Methyl Viologen Films at Gold Electrodes" Bull.Korean Chem.Soc.15. 190-191 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Kitamura: "Effect of Complexation by Cyclodextins on the Voltammetric Characteristic of Viologens Adsorbed on a HMDE" J.Electroanal.Chem.368. 281-284 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Kitamura: "FT-IRAS Sudy of p-Cyanobenzoate Adsorpion on a Polycrystalline Gold Electrode" J.Electrochem.Soc.Jpn.(Denki kagaku). 62. 532-533 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Tsushima: "Use of Hydrodynamic Chronocoulometry for Simultaneous Determination of Diffusion Coefficients and Concentrations of Dioxygen in Various Media" Anal.Chem.66. 4551-4556 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ohsaka: "Mediated Electron-Transfer of Poly-(ethylene) Oxide-Modified Superoxide Dismutase by Methyl Viologen" Bioelectrochem.& Bioenerg.37. 73-76 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Matsumoto: "Electrogeneration of Superoxide Ion on Thiophenol-Modified Gold Electrode in Aqueous Solution" J.Electrochem.Soc.Jpn.(Denki kagaku). 63, No.12. 1205-1208 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tokuda: "AC Voltammetry at Microcylinder Electrodes" J.Electroanal.Chem.396. 365-370 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Oyama: "Coupling between Electron and Mass Transfer Kinetics in Electroactive Polymer Films. An Application of in situ Quartz Crystal Electrode (QCE)." Progress in Polym.Sci.20. 761-818 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Satoh: "Observation of Intermolecular Charge-Transfer Spectra for Propyl Viologen Dihalides in a Series of Polyether Media" Chem.Lett.51-52 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Matsumoto: "Electrogeneration of Superoxide Ion at Mercury Electrodes with a Hydrophobic Adsorption Film in Aqueous Media" Electroanalysis. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Matsumoto: "Electrogeneration of superoxide Ion at alpha-Quinoline-Adsorbed mercury Electrode in Alkaline Aqueous Solution" J.Deuterium Sci.(in press).

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1997-03-04  

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