• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

酸素の4電子還元および水の4電子酸化触媒系の開発と水の光完全分解への展開

Research Project

Project/Area Number 03J04315
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Research Field 物質変換
Research InstitutionOsaka University

Principal Investigator

岡本 健  大阪大学, 大学院・工学研究科, 特別研究員(DC1)

Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 2004: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2003: ¥1,500,000 (Direct Cost: ¥1,500,000)
Keywords電子移動反応 / 光合成 / 呼吸鎖 / 金属イオン / 酸素 / 共有結合 / 非共有結合 / 光エネルギー / 水 / 還元
Research Abstract

我々の生命活動を支える非常に重要な過程として光合成と呼吸がある。近年、枯渇する化石エネルギーに替わるエネルギー源を早急かつ効率的に得ることが求められている。そこで、光合成系や呼吸鎖のように励起状態および基底状態の電子移動過程を緻密に制御することによりクリーンな物質変換を伴う高効率エネルギー変換系を構築することが焦眉な課題となっている。そこで本研究では、高効率エネルギー変換系を開発することを目指して、共有結合と非共有結合により高度に制御された電子移動系の構築を行ったものである。主な成果は次のように大きく3つに要約される。
1.天然の電荷分離系を凌駕する超長寿命電荷分離状態を実現するドナー・アクセプター連結2分子系の開発に成功している。さらに非共有結合を利用することにより、電荷分離寿命を顕著に長寿命化できることを初めて見出している。
2.生体内で重要な役割を果たしている水素結合、金属イオン、アンモニウムイオン、さらにダイマーラジカルアニオン錯体形成による電子移動反応の活性化や制御の効果を初めて定量的に明らかにしている。
3.我々の生命活動において、非常に重要な過程である酸素の4電子還元反応の制御とその反応機構の解明に成功している。
以上のように、本研究はクリーンな物質変換を伴うエネルギー変換系を効率良く構築している自然界の光合成と呼吸鎖に注目し、共有結合と非共有結合を利用した光電荷分離状態の長寿命化とその応用、電子移動反応における非共有結合による活性化と制御、さらに多電子移動過程の金属錯体による精密制御に成功している。本研究の成果はエネルギー・環境問題の解決に向けた重要なステップとなる。

Report

(2 results)
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (21 results)

All 2005 2004 2003 Other

All Journal Article (12 results) Publications (9 results)

  • [Journal Article] Hydrogen Bonds Not Only Provide a Structural Scaffold to Assemble Donor and Acceptor Moieties of Zinc Porphyrin-Quinone Dyads but Also Control the Photoinduced Electron Transfer to Afford the Long-Lived Charge-Separated States2005

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Phys. Chem. B 109(in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A Drastic Difference in Lifetimes of the Charge-Separated State of Formanilide-Anthraquinone Dyad vs Ferrocene-Formanilide-Anthraquinone Triad and Their Photoelectrochemical Properties of the Composite Films with Fullerene Clusters2005

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Phys. Chem. B 109(in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Mechanism of Four-Electron Reduction of Dioxygen to Water by Ferrocene Derivatives in the Presence of Perchloric Acid in Benzonitrile Catalyzed by Cofacial Dicobalt Porphyrins.2004

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Am. Chem. Soc. 126

      Pages: 10441-10449

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Dehydrogenation versus Oxygenation in Two-Electron and Four-Electron Reduction of Dioxygen by 9-Alkyl-10-methyl-9,10-dihydroacridines Catalyzed by Monomeric Cobalt Porphyrins and Cofacial Cobalt Porohyrins in the Presence of Perchloric Acid.2004

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Am. Chem. Soc. 126

      Pages: 17059-17066

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Remarkable Accelerating Effects of Ammonium Cations on Electron-Transfer Reactions of Quinones by Hydrogen Bonding with Semiquinone Radical Anions.2004

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Phys. Chem. A 108

      Pages: 10405-10413

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Effects of Metal Ions on Photoinduced Electron Transfer in Zinc Porphyrin-Naphtaleneimide Linked Systems.2004

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      Chem. Eur. J. 10

      Pages: 474-483

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A Dramatic Elongation of the Lifetime of Charge-Separated State by Complexation with Yttrium Triflate in Ferrocene-Anthraquinone Linked Dyad.2004

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Am. Chem. Soc. 126

      Pages: 56-57

    • Related Report
      2004 Annual Research Report
  • [Journal Article] An Yttrium Ion-Selective Fluorescence Sensor Based on Metal Ion-Controlled Photoinduced Electron Transfer in Zinc Porphyrin-Quinone Dyad.2004

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Am. Chem. Soc. 126

      Pages: 13922-13923

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Effects of Hydrogen Bonding on Metal-Ion Promoted Intramolecular Electron Transfer and Photoinduced Electron Transfer in a Ferrocene-Quinone Dyad with a Rigid Amide Spacer.2003

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Am. Chem. Soc. 125

      Pages: 1007-1013

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Formation of a Supramolecular Porphyrin-Spacer-Acceptor Ternary Complex and Intracomplex Electron Transfer.2003

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Phys. Chem. A 107

      Pages: 379-385

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Metal Ion-Promoted Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad Continuous Change in Driving Force and Reorganization Energy with Metal Ion Concentradon.2003

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Phys. Chem. A 125

      Pages: 7014-7021

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Self-Promoted Electron Transfer from Cobalt(II) Porphyrin to p-Fluoranil to Produce Dimer Radical Anion-Cobalt(III) Porphyrin Complex.2003

    • Author(s)
      Okamoto, K., et al.
    • Journal Title

      J. Am. Chem. Soc. 125

      Pages: 12426-12427

    • Related Report
      2004 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Thermal Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad Promoted by Metal Ions."Angew.Chem.Int.Ed.. 41. 620-622 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Hydrogen-Bonding Dynamics in Photoinduced Electron transfer in a Ferrocene-Quinone Linked Dyad with a Rigid Amide Spacer."J.Am.Chem.Soc.. 124. 6794-6795 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Uphill photooxidation of NADH Analogues by Hexyl Viologen Catalyzed by Zinc Porphyrin-Linked Fullerenes."J.Phys.Chem.A. 106. 1903-1908 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Effects of Hydrogen Bonding on Metal-Ion Promoted Intramolecular Electron Transfer and Photoinduced Electron Transfer in a Ferrocene-Quinone Dyad with a Rigid Amide Spacer."J.Am.Chem.Soc.. 125. 1007-1013 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Formation of a Supramolecular Porphyrin-Spacer-Acceptor Ternary Complex and Intracomplex Electron Transfer"J.Phys.Chem.A. 107. 379-385 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Metal Ion-Promoted Intramolecular Electron Transfer in a Ferrocene-Naphthoquinone Linked Dyad Continuous Change in Driving Force and Reorganization Energy with Metal Ion Concentration."J.Am.Chem.Soc.. 125. 7014-7021 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Self-Promoted Electron Transfer from Cobalt(II) Porphyrin to p-Fluoranil to Produce Dimer Radical Anion-Cobalt(III) Porphyrin Complex."J.Am.Chem.Soc.. 125. 12426-12427 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "Control of Lifetime for Photoinduced Charge Separated States by Metal Ions in Porphyrin-Naphtaleneimide Linked Dyads."Chem.Eur.J. 10. 474-483 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Okamoto, K. et al.: "A Dramatic Elongation of the Lifetime of Charge-Separated State by Complexation with Ytterium Triflate in Ferrocene-Anthraquinone Linked Dyad."J.Am.Chem.Soc.. 126. 56-57 (2004)

    • Related Report
      2003 Annual Research Report

URL: 

Published: 2003-04-01   Modified: 2024-03-26  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi