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Design on Photoredox Reaction Systems by Use of Functional Polymers

Research Project

Project/Area Number 59430019
Research Category

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

Allocation TypeSingle-year Grants
Research Field 高分子合成
Research InstitutionOsaka University

Principal Investigator

NOZAKURA Shun-ichi  Faculty of Science, Osaka University, 理学部, 教授 (90028085)

Co-Investigator(Kenkyū-buntansha) FURUE Masaoki  Faculty of Science, Osaka University, 理学部, 助手 (30028245)
MORISHIMA Yotaro  Faculty of Science, Osaka University, 理学部, 講師 (70028249)
Project Period (FY) 1984 – 1986
Project Status Completed (Fiscal Year 1986)
Budget Amount *help
¥21,100,000 (Direct Cost: ¥21,100,000)
Fiscal Year 1986: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1985: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1984: ¥16,800,000 (Direct Cost: ¥16,800,000)
KeywordsAmphiphilic polyelectrolyte / Photo-induced electron transfer / Charge separation / Local electric Potential / Hydrophobic interaction / Organized structure / Collisionless electron transfer / 電子移動理論 / 両親媒性高分子電解貭 / クロモホア / 分子設計 / 励起状態自己失活 / 静電ポテンシャル / クロモホア個室化 / 疎水性ミクロドメイン
Research Abstract

Amphiphilic polyelectrolytes consisting of hydrophobic chromophores(polycyclic aromatics or organic dyes) and charged groups create an organized structure in aqueous solution as a result of microphase separation. Laser photolysis studies revealed that a strong electrostatic potential around the hydrophobic microdomain resulted in an efficient charge separation in photo-induced electron transfer reaction. It was also revealed that the hydrophobic microdomains effectively associated with reaction partners, electron donors or acceptors to or from the excited chromophores within the microdomains, in the aqueous system, and thus the forward electron transfer reaction could be largely enhanced.
The structural organization of the amphiphilic polyelectrolytes occurs due to a hydrophobic association. Hydrophobic groups with <pi> -electron systems in the amphiphilic polyelectrolytes were found to be easier to self-aggregate than those with <sigma> -electron systems. A thermodynamical study suggested that the planar structure of the hydrophobic groups with the <pi> -system would fit tightly to each other in the hydrophobic interaction to release a large amount of free water, thus leading to a large positive entropy as compared with those with the <sigma> -system.
Chromophores covalently linked to a polyelectrolyte were "compartmentalized" in the hydrophobic aggregates of pendant photo-inactive hydrophobic groups. A collisionless long-range electron transfer that occurs in this system showed that the back electron transfer was slower than the forward reaction by a factor of several orders of magnitude. This is interpreted to be due to the "inverted region" of electron transfer theory.

Report

(2 results)
  • 1986 Final Research Report Summary
  • 1985 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 森島洋太郎: J.Phys.Chem.89. 4081-4087 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 森島洋太郎: J.Polym.Sci.,Polym.Symp.74. 1-15 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 小林高臣: J.Polym.Sci.,Polym.Chem.Ed.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 森島洋太郎: Macromolecules.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 森島洋太郎: Macromolecules.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Yotaro Morishima: "Kinetic Analysis of the Anomalous Behavior in the Fluorescence Quenching of Phenanthryl Groups Covalently Linked to Polyelectrolytes" J. Phys. Chem.,. 89. 4081-4087 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Yotaro Morishima: "Photoredox Reaction of Functionalized Polyelectrolytes" J. Polym. Sci., Polym. Symp.,. 74. 1-5 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Yotaro Morishima: "Preferential Excimer Emission from Amphiphilic Alternating Copolymers of 2-Vinylnaphthalene and Maleic Acid in Aqueous Solution" Macromolecules.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Yotaro Morishima: "Intramolecular Compartmentalization of Photoredox Centers in Functionalized Amphiphilic Polyelectrolytes: A Model for Collisionless Electron Transfer Systems" Macromolecules.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Yotaro Morishima: "Electrostatic Potential and Polarity at the Molecular Surface of Polyelectrolytes As Probed by pH-sensitive Chromophores Covalently Attached to the Mainchain"

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] The Journal of Physical Chemistry. 89巻-19号. (1985)

    • Related Report
      1985 Annual Research Report
  • [Publications] Photochemistry and Photobiology. 42巻-5号. (1985)

    • Related Report
      1985 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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