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2006 Fiscal Year Final Research Report Summary

Mechanistic Studies of Photoinduced Electron Transport across Vesicle Bilayers

Research Project

Project/Area Number 16550030
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

MURATA Shigeru  The Univ.of Tokyo, Dep.of Arts and Sciences, Associate Prof., 大学院総合文化研究科, 助教授 (40192447)

Project Period (FY) 2004 – 2006
KeywordsPhotoinduced electron transfer / Lipid bilayer membranes / Pyrene derivatives / Photoenergy conversion / Vesicles
Research Abstract

Endoergic electron transport across vesicle bilayers from ascorbate (Asc^-) in the inner waterpool to methylviologen (MV^<2+>) in the outer aqueous solution was driven by the irradiation of pyrene derivatives embedded in the vesicle bilayers. The initial rate of MV^<2+> reduction is dependent on the substituent group on the pyrenyl ring ; a hydrophilic functional group linked with the pyrenyl ring by a short methylene chain acts as a sensitizer for the electron transport. Mechanistic studies suggests that the electron transport is mainly initiated by the reductive quenching of the singlet excited state of pyrene by Asc^- and proceeds by a mechanism involving electron exchange between the pyrenes located at the inner and outer interface across the vesicle bilayer. Novel unsymmetrically substituted pyrenes having both a hydrophilic group linked by a short methylene chain and a hydrophobic long alkyl group was designed and synthesized, which acted as an excellent sensitizers for the electron transport across vesicle bilayers. Moreover, in order to enhance the electron transport efficiency, the effects of molecular structure of lipids and electron donors incorporated in the inner waterpool on the MV^<2+> reduction rate were investigated. The use of newly synthesized dimeric pyrenes bridged by a long alkyl chain as sensitizers resulted in the enhancement of electron transport efficiency. Although these systems unfortunately cannot work using visible light, it appears to be one of the most faithful model of natural photosynthesis in that an electron is transferred with the aid of light energy between two reversible redox couples in the energetically uphill direction through lipid bilayer walls preventing a charge recombination.

  • Research Products

    (6 results)

All 2007 2006 2005

All Journal Article (6 results)

  • [Journal Article] Amphiphilic Pyranines : Chromophore Wrapped in a Hydrophobic Alkyl Chain and Micelle Formation Induced by Complexation with MV^<2+>2007

    • Author(s)
      R.Sasaki
    • Journal Title

      Chemistry Letters 36・3

      Pages: 364-365

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Amphiphilic Pyranines : Chromophore Wrapped in a Hydrophobic Alkyl Chain and Micelle Formation Induced by Complexation with MV^<2+>2007

    • Author(s)
      R.Sasaki
    • Journal Title

      Chem.Lett. 36(3)

      Pages: 364-365

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Pyrene-Sensitized Electron Transport across Vesicle Bilayers : Dependence of Transport Efficiency of Pyrene Substituents2006

    • Author(s)
      T.Mizushima
    • Journal Title

      Organic & Biomolecular Chemistry 4・11

      Pages: 4336-4344

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Pyrene-Sensitized Electron Transport across Vesicle Bilayer : Dependence of Transport Efficiency of Pyrene Substituents2006

    • Author(s)
      T.Mizushima
    • Journal Title

      Org.Biomol.Chem. 4(11)

      Pages: 4336-4344

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Oxidative Formation of Thiolesters in a Model System of the Pyruvate Dehydrogenase Complex2005

    • Author(s)
      Y.Kageyama
    • Journal Title

      Journal of Organic Chemistry 70・8

      Pages: 3140-3147

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Oxidative Formation of Thiolesters in a Model System of the Pyruvate Dehydrogenase Complex2005

    • Author(s)
      Y.Kageyama
    • Journal Title

      J.Org.Chem. 70(8)

      Pages: 3140-3147

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

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Published: 2008-05-27  

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