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1996 Fiscal Year Final Research Report Summary

Analysis of Electron Transfer Reactions in Solution with the Development of High-Sensitive Detection Method for Electrogenerated Chemiluminescence using Flow-Electrolysis.

Research Project

Project/Area Number 07555567
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section試験
Research Field 工業分析化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

OYAMA Munetaka  Kyoto University, Graduate School of Engineering Instructor, 工学研究科, 助手 (90221861)

Co-Investigator(Kenkyū-buntansha) NAGAMURA Toshihiko  Unisoku Co.Ltd.Head of Research Division, 研究所長
Project Period (FY) 1995 – 1996
KeywordsElectrogenerated Chemiluminescence / Ion Radicals / Electrolysis Stopped-Flow Method / column Electrode / Pulse Electrolysis
Research Abstract

New method for the measurement of electrogenerated chemiluminescence (ECL) was developed by using a pulse-electrolysis stopped-flow method. While numerous studies have been devoted to the ECL caused in the reactions between cation and anion radicals of aromatic substances in aprotic solvents, the ECL reactions ever observed have been resticted to the systems having a smaller redox potential differences than those of a molecule concerned. These are so called "energy deficient" systems. By contrast, for example, the pure reaction between diphenylanthracene (DPA) cation radical and pyrene (PY) anion radical has been very difficult to be observed in the conventional methods because of the interference by the reduction of DPA which is concurrent with the reduction of PY.Although this sort of "energy sufficient" reaction has never been observed, its measurement will be effective to study the emission directly from the singlet state (S-route) and to obtain the information on the excited states explicity. In the present work, the ECL measurement on the energy sufficient systems composed of different kind of ion radicals has become possible by using a pulse-electrolysis stopped-flow apparatus having two electrolysis lines. In this apparatus, by generating cation radicals and anion radicals independently, the ECL is observed in an optical cell. Therefore, various reactions of the energy sufficient systems composed of different kind of ion radicals can be targeted including sort-lived species. In the reaction between thianthrene cation radical and PY anion radical, it was found that the emision spectra changed with the addition of the precursors reflecting the complex electron and energy transfers in solution. In addition, the emitting properties was clarified to depend on the sort of the molecules significantly through the measurements in which three Components were mixed.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] M. Oyama: "Solvent effect on the ionpair formation between 2, 3, 5, 6-tetrachloro-1, 4-benzoquinolle ahion radical and Mg^<2+> measured using a pulse elecholysis stopped floro method" J. Electroanal. Chem.401. 243-246 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Oyama: "Thin Layer Electrochemical Resonance Raman Measurement for Complex Electrode Reactions." J. Chem. Soc. Chem. Commun.1035-1036 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 小山宗孝: "ラマン分光法による炭素電極表面の解析" 化学と工業. 49. 801- (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Yamanuki: "Resonance Raman measurement for anthracent derivative cation and anion radicals using a column-electrolytic continuous-flow method" Vibrational spectroscopy. 13. 205-211 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Oyama: "Detailed Analysis of Reaction Kinetics and Mechanisms of Electrogenerated Tetramethoxy thianthrene Cation Radical and Dication" J. Electroanal. Chem.(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Nagaoka: "Soluble Polyaniline as an Intelligent Exchanger for Inorganic and Organic Anions." Anal. Chem.(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Oyama: "Solvent effect on the ion pair formation between 2,3,5,6-tetrachloro-1,4-benzoquinone anion radical and Mg^<2+> measured using a pulse electrolysis stopped flow method" J.Electroanal.Chem.401. 243-246 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Oyama: "Thin Layr Electrochemical Resonance Raman Measurement for Complex Electrode Reactions" J.Chem.Soc.Chem.Comm. 1035-1036 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Oyama: "Analysis of Carbon Electrode Surfaces by Using Raman Spectroscopy" Kagaku to Kogyo. 49. 801 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Yamanuki: "Resonance Raman measurement of anthracene derivative cation and anion radicals using a column-electrolytic continuous-flow method" Vibrational Spectroscopy. 13. 205-211 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Oyama: "Detailed Analysis of Reaction Kinetics and Mechanisms of Electrogenerated Tetramethoxythianthrene Cation Radical and Dication" J.Electroanal.Chem.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Nagaoka: "Soluble Polyaniline as an intelligent Exchanger for Inorganic and Organic Anions" Anal.Chem.(in press).

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

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Published: 1999-03-09  

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