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1999 Fiscal Year Final Research Report Summary

Development of Frequency Swept EPR under the Low Magnetic Field

Research Project

Project/Area Number 10044057
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research
Research Field Inorganic chemistry
Research InstitutionTohoku University

Principal Investigator

YAMAUCHI Seigo  Tohoku University, Institute for Chemical Reaction Science, Professor, 反応化学研究所, 教授 (10127152)

Co-Investigator(Kenkyū-buntansha) UNNO Masashi  Tohoku University, Institute for Chemical Reaction Science, Research Associate, 反応化学研究所, 助手 (50255428)
OHBA Yasunori  Tohoku University, Institute for Chemical Reaction Science, Associate Professor, 反応化学研究所, 助教授 (10176985)
Project Period (FY) 1998 – 1999
KeywordsHigh frequency EPR / Time-resolved EPR / Excited quintet state / Excited quartet state / Molecular motion / Two dimensional EPR / Heme protein / Resonance Raman spectroscopy
Research Abstract

Collaborative studies were made by use of two techniques, electron paramagnetic resonance(EPR) and vibrational (Raman) spectroscopy, giving the following results.
For EPR, we collaborated with four laboratories, Prof.Moebius's at Free University of Berlin, Prof.Corvaja's at Padova University in Italy, Prof.Levanon's at Hebrew University of Jerusalem, and Prof.Kothe's at Freiburg University in Germany, where we made the experiments and discussion. For Raman, Dr.Unno visited Prof.Champion's lab. at Northeastern University of Boston and ran experiments for two weeks.
1. In a system of metallo(Zn and Mg) porphyrin-nitroxide radical, we observed excited doublet and quartet states for the first time by EPR techniques, which are separated nicely by means of high frequency (95 GHz) EPR.
2. EPR signals of the excited triplet states were observed for the first time in solution using metallo-porphyrins and -phthalocyanines up to +90℃. From the spectral simulation, averaging over the Jahn-Teller split states and molecular motions were analyzed , which indicates that this method is very useful for analyses of excited triplet properties in solution.
3. Two dimensional (2D) pulsed EPR techniques were developed to determine spin multiplicity of the excited multiplet states and applied to studies in systems of bisradical linked fullerene. On excitation the excited quintet states were observed and definitely assigned for the first time and the electronic structures were analyzed.
4. The resonance Raman investigation was made for oxygenated cytochrome P450 and a structural marker band was successfully assigned at the active site. The observation of the Fe-O-O bending mode reveals structural specificity of the enzyme.

  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] T.Funayama et al.: "Studies of the Lowest Excited Triplet State of [Pt(i-biq)(CN)2] by means of Time-Resolved EPR and Optical Spectroscopy"Bull.Chem.Soc.Jpn.. 73. 1541-1550 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] F.Conti et al.: "Studies on a Bisitroxide Fullerene Derivative in the Ground Triplet and First Photoexcited Quintet States"J.Phys.Chem.A.. 104. 4962-4967 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Unno et al.: "Evidence for a Protonated and cis Configuration Chromophore in the Photobleached Intermediate of Photoactive Yellow Protein"J.Am.Chem.Soc.. 112. 4233-4234 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Unno et al.: "Identification of the Fe-O-O Bending Mode in Oxycytochrome P450cam by Resonance Raman Spectrosocy"J.Am.Chem.Soc.. 121. 376-380 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] J.Fujisawa et al.: "First Observation of the Excited Doublet State of a Radical-Triplet Pair in Solution : W-band Time-Resolved Electron Paramagnetic Resonance Spectroscopy"J.Phys.Chem.A.. 103. 213-216 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] J.Fujisawa et al.: "Pulsed and cw-Time-Resolved EPR Studies of Photoinduced Electron Transfer between Zn(II) Porphyrin and Fullerene"Chem.Phys.Lett.. 294. 248-254 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Hirota,S.Yamauchi: "Dynamic Spin Chemistry"Kodansha. 61 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Murai,S.Tero-Kubota,S.Yamauchi: "Specialist Periodical Reports : Electron Spin Resonance"The Royal Society of Chemistry, Cambridge, UK. 33 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Funayama, M.Kato, H.Kosugi, M.Yagi, J.Higuchi, and.Yamauchi: "Studies of the Lowest Excited Triplet State of [Pt(ibiq)(CN)_2] by means of Time-Resolved EPR and Optical Spectroscopy"Bull.Chem.Soc.Jpn.. 73. 1541-1550 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Conti, C.Corvaja, A.toffoletti, N.Mizuochi, Y.Ohba, and S.Yamauchi: "Studies on a Binitroxide Fullerene Derivative in the Ground Triplet and First Photoexcited Quintet States"J.Phys.Chem.A.. 104. 4962-4967 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Unno, M.Kumauchi, J.Sasaki, F.Tokunaga, and S.Yamauchi: "Evidence for a Protonated and cis Configuration Chromophore in the Photobleached Intermediate of Photoactive Yellow Protein"J.Am.Chem.Soc.. 112. 4233-4234 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Satoh, Y.Ohba, M.Hoshino, S.Konishi, F.Ebina, S.Yamauchi, and M.Iwaizumi: "Electronic States and Magnetic Properties of Triplet Porphyrinato Copper(II) Cation Radical Complexes"Bull.Chem.Soc.Jpn.. 72. 2389-2394 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Mizuochi, Y.Ohba, S.Yamauchi: "First Observation of the Photoexcited Quintet State in Fullerene Linked with Two Nitroxide Radicals"J.Phys.Chem.A.. 103. 7749-7752 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N.Mizuochi, Y.Ohba, S.Yamauchi: "The Structure and Electronic State of Photoexcited Fullerene Likned to a Nitroxide Radical Studied by an Analysis of 2D Electron Paramagnetic Resonance Nutation Spectrum"J.Chem.Phys.. 111. 3479-3484 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] I.SM Saiful, J.Fujisawa, N.Kobayashi, Y.Ohba, and S.Yamauchi: "A Study of Electron Polarization Transfer in a System of Photo-Excited Triplet Phthalocyanine and a Nitroxide Radical"Bull.Chem.Soc.Jpn.. 72. 661-667 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J.Fujisawa, K.Ishii, Y.Ohba, S.Yamauchi, M.Fuhs, and K.Mobius: "First Observation of the Excited Doublet State of a Radical-Triplet Pair in Solution : W-band Time-Resolved Electron Paramagnetic Resonance Spectroscopy"J.Phys.Chem.A.. 103. 213-216 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J.Fujisawa, Y.Ohba, and S.Yamauchi: "Pulsed and cw-Time-Resolved EPR Studies of Photoinduced Electron Transfer between Zn(II) Porphyrin and Fullerene"Chem.Phys.Lett.. 294. 248-254 (1998)

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

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Published: 2002-03-26  

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