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Formation of Porphyrin Fiber and Control of Its Electronic Process by Photon Injection

Research Project

Project/Area Number 11650935
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子構造・物性(含繊維)
Research InstitutionWaseda University

Principal Investigator

KOMATSU Teruyuki  Waseda University, Advanced Research Institute for Science and Engineering, Lecturer, 理工学総合研究センター, 講師 (30298187)

Co-Investigator(Kenkyū-buntansha) YANAGIMOTO Tetsuya  Waseda University, Faculty of Science and Engineering, Research Associate, 理工学部, 助手 (70318781)
TSUCHIDA Eishun  Waseda University, Faculty of Science and Engineering, Professor, 理工学部, 教授 (90063461)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 2000: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1999: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsLipidporphyrin / Molecular Assembly / Porphyrin Molecular Fiber / Dioxygen Coordination / Phorpholipid Vesicle / Electronic Process / Photoreduction / LMCT Absorption / リピドポルフィリン鉄 / 自己組織化 / ポルフィリン分子繊維 / LMCT / ヒアルロン酸 / 過渡吸収スペクトル / 量子収率 / リピドポルフィリン
Research Abstract

In order to revive the dioxygen-coordination ability of the self-organized lipidporphyrinatoiron assemblies, two non-enzymatic systems to reduce the oxidized ferric metal centers have been constructed, and their mechanisms were studied.
First, a new lipidporphyrin with a covalently bound axial imidazole has been synthesized. It was self-organized in aqueous media to give fibrous aggregate (10 nm width). The AFM measurement in liquid phase revealed that four porphyrin molecules continuously aligned at the fiber's core, which can reversibly bind and release dioxygen under physiological conditions. The resonance Raman spectroscopy showed the coordination structure of the dioxygen, and the dioxygen-binding affinity and dioxygen association and dissociation rate constants were also measured.
Photoirradiation of phospholipid vesicle embedding lipidporphyrinatoiron(III) and lipidporphyrinato-zinc(II) (30-40 nmφ) induced electron transfer from the excited zinc(II) center to the Fe(III) complex. Under the coexistence of triethanolamine, the ratio of the ferrous complex increased and it can bind dioxygen.
On the other hand, saline solution of lipidporphyrinatoiron(III) showed a ligand-to-metal charge transfer (LMCT) absorption band at 362 nm. Under the presence of small amount of saccharides (hyaluronic acid, glucose, etc.), LMCT irradiation (365 nm) led to reduction of the central ferric iron(III), giving ferrous high-spin complex. This photoreduction involves fast intramolecular electron transfer, and the saccharide itself is oxidized to prevent the back electron transfer reaction. The result of the laser-flash photolysis showed that the formation of the ferrous high-spin complex occurred within 100 ns. The obtained Fe(II) complex formed a stable dioxygen adduct complex.
Furthermore, this photoreduction system could be applied to the albumin-porphyrinatoiron(III) hybrid, in which albumin played the role of the electron donner.

Report

(3 results)
  • 2001 Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] T.Komatsu et al.: "Self-Assembled Fibers Made of Lipidporphyrinato-Zinc(II) and -Iron(II) Complexes with an Intramolecular Coordinated Axial Imidazole"Langmuir. 15. 4427-4433 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] E.Tsuchida et al.: "Molecular Environment Effect on O_2-Binding to Lipidporphyrinatoiron(II) Complexes in Aqueous Media"Journal of Porphyrins and Phthalocyanines. 4. 81-87 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Komatsu et al.: "Photoreduction of Self-assembled Lipidporphyrinato-iron(III) Chloride with Hyaluronic Acid under Semi-Physiological Conditions"Chemistry Letters. 305. 84-85 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Yanagimoto et al.: "Photoinduced Electron Transfer between Lipidporphyrinato-zinc(II) and -Iron(III) Complexes in Phospholipid Vesicular Membrane"Inorgica Chmica Acta. 15. 26-31 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Nakagawa et al.: "Photoreduction of Autooxidized Albumin-heme Hybrid in Saline Solution"Bioconjugate Chemistry. 12. 648-652 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Yanagimoto et al.: "Photoreduction of a Self-Assembled (Lipidporphyrinato)iron(III) Complex in Saline by LMCT Excitation: Co-Aggregated Hyaluronic Acid Allows an Irreversible Electron Transfer"Bulletin of Chemical Society, Japan. 74. 2123-2128 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Komatsu, T. Yanagimoto. Y. Furubayashi, J. Wu, E. Tsuchida: "Self-Assembled Fibers Made of Lipidporphyrinnato-zinc(II) and -iron(II) Complexes with an Intramolecular Coordinated Axial Imidazole"Langmuir.. 15. 4427-4433 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] E. Tsuchida, T. Komatsu, T. Yanagimoto: "Molecular Environment Effect on O_2-Binding to Lipidporphyrinatoiron(II) Complexes in Aqueous Media"J. Porphyrins and Phthalocyanines. 4. 81-87 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Komatsu, T. Yanagimoto, A. Nakagawa, E. Tsuchida: "Photoreduction of Self-assembled Lipidporphyrinatoiron(III) Chloride with Hyaluronic Acid under Semi-physiological Conditions"Chem. Lett.. 2000. 84-85 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Yanagimoto, T. Komatsu, E. Tsuchida: "Photoinduced Electron Transfer between Lipidporphyrinato-zinc(II) and -iron(III) Complexes in Phospholipid Vesicular Membrane"Inorg. Chim. Acta.. 305. 26-31 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A. Nakagawa, T. Komatsu, E. Tsuchida: "Photoreduction of Autooxidized Albumin-heme Hybrid in Saline Solution : Revival of Its O_2-Binding Ability"Bioconjugate Chem.. 12. 648-652 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Yanagimoto, A. Nakagawa, T. Komatsu, E. Tsuchida: "Photoreduction of a Self-assembled (Lipidporphyrinato) iron(III) Complex in Saline by LMCT Excitation : Co-aggregated Hyaluronic Acid Allows an Irreversible Electron Transfer"Bull. Chem. Soc. Jpn.. 74. 2123-2128 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Komatsu et al.: "Redox Behavior of Human Serum Albumin-Heme Hybrid on Graphite Electrode Modified with Didodecyldimethylammonium Bromide"Chemistry Letter. 2000. 1194-1195 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Komatsu et al.: "Kinetics of CO and O_2 Binding to Human Serum Albumin-Heme Hybrid"Bioconjugate Chemistry. 11. 772-776 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Komatsu et al.: "Photoreduction of Autooxidiazed Albumin-Heme Hybrid in Saline Solution ; Revival of Its O_2-Binding Ability"Bioconjugate Chemistry. 11(印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Komatsu et al.: "Molecular Environment Effect on O_2-Binding to Lipid-porphyrinatoiron (II) Complexes in Aqueous media"Journal of Porphyrins and Phthalocyanines. 4. 81-87 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Komatsu et al.: "Photoreduction of Self-Assembled Lipidporphyrinato-Iron (III) Chloride with Hyaluronic Acid under Semi-physiological Conditions"Chemistry Letter. 2000. 84-85 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Komatsu et al.: "Photoinduced Electron Transfer between Lipidporphyrinato-Zinc (II) and Iron (III) Complexes in Phospholipid Vesicular Membrane"Inorganica Chimica Acta. (in press)(印刷中). (2000)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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