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Development of a New Two-dimensional Pulsed EPR Method and an Application to Heme-proteins

Research Project

Project/Area Number 11640495
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionInstitute for Chemical Reaction Science, Tohoku University

Principal Investigator

OHBA Yasunori  Tohoku University, Institute for Chemical Reacton Science, Associated Professor, 反応化学研究所, 助教授 (10176985)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2000: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1999: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywordselectron paramagnetic resonance / electron spin resonance / nutation spectrum / heme protein / myoblobin / pulsed EPR / 電子常時性共鳴
Research Abstract

A new technique of two-dimensional nutation spectroscopy for a disordered system with large g-anisotropy was developed. This method is based on the fact that a nutational frequency is determined by the g value which belongs to the direction perpendicular to the external magnetic field. The method enables one to determine a very small g-value (typically less than 1) and relative sign of g-principal values. The method is applied to low-spin met myoglobin from horse heart.
1. The most important part of the pulsed EPR instrument for the nutational experiment is the microwave resonator. A strong and homogeneous microwave field is essential. A loop-gap resonator was compared with a rectangular cavity resonator. A stable sample holder of a loop-gap resonator for helium temperature measurements was designed and constructed.
2. A nutation signal from a disordered sample was analyzed by a spectral simulation technique. A gated integration and ESE-FT methods were compared as a detection technique. The analysis showed that there was some distortion and shift of a spectrum in a gated integration caused by off-resonance effects. These artifacts could be removed by the ESE-FT technique.
3. Two-dimensional nutation spectra were observed for low-spin horse heart met-myoglobin in frozen solution. By means of the ESE-FT technique, the nutation spectra those were free from off-resonance effects were obtained. The spectra were compared with theoretical predictions for magnetic field dependence of a nutational spectrum. It is confirmed that a nutation frequency was determined by the g-principal value of the direction orthogonal to the external magnetic field. The very small g-value of cyanide ion complex, g=0.93, could be observed by this method.
4. It was predicted by the theoretical analysis that relative sign of g-principal values could be determined by a nutation spectrum from a disordered system.

Report

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

    (15 results)

All Other

All Publications (15 results)

  • [Publications] Y.Ohba: "Utilization of characteristics of fast linear prediction based on the lattice algorithm in an analysis of time domain magnetic resonance"Spect.Chim.Acta,A. 56. 235-243 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] F.Conti, et al.: "EPR studies on a binitroxide fullerene derivative in the ground triplet and first photoexcited quintet state"J.Pyhs.Chem.A. 104. 4962-4967 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Nakamura, et al.: "Identification of copper ligands in Aspergillus oryzae tyrosinase by site-directed mutagenesis"Biochem.J.. 350. 537-545 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] N.Mizuochi, et al.: "The Structure and Electronic State of Photoexcited Fullerene Linked to a Nitroxide Radical Studied by an Analysis of a 2D Electron Paramagnetic Resonance Nutation Spectrum,"J.Chem.Phys.. 111. 3479-3484 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] N.Mizuochi, et al.: "First Observation of the Photoexcited Quintet State in Fullerene Linked with Two Nitroxide Radicals"Phys.Chem.A. 103. 7749-7752 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohba: "Utilization of characteristics of fast linear prediction based on the lattice algorithm in an analysis of time domain magnetic resonance"Spect.Chim.Acta, A. 56. 235-243 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] F.Conti, et al.: "EPR studies on a binitroxide fullerene derivative in the ground triplet and first photoexcited quintet state"J.Pyhs.Chem.A. 104. 4962-4967 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Nakamura, et al.: "Identification of copper ligands in Aspergillus oryzae tyrosinase by site-directed mutagenesis"Biochem.J.. 350. 537-545 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] N.Mizuochi, et al.: "The Structure and Electronic State of Photoexcited Fullerene Linked to a Nitroxide Radical Studied by an Analysis of a 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
    • Related Report
      2000 Final Research Report Summary
  • [Publications] N.Mizuochi, et al.: "First Observation of the Photoexcited Quintet State in Fullerene Linked with Two Nitroxide Radicals"Phys.Chem.A. 103. 7749-7752 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Ohba: "Utilization of characteristics of fast linear prediction based on the lattice algorithm in an analysis of time domain magnetic resonance"Spect.Chim.Acta,. A,56,. 235-243 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] F.Conti, et al.: "EPR studies on a binitroxide fullerene derivative in the ground triplet and first photoexcited quintet state"J.Pyhs.Chem.. A104. 4962-4967 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Nakamura, et al.: "Identification of copper ligands in Aspergillus oryzae tyrosinase by site-directed mutagenesis"Biochem.J.. 350. 537-545 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Mizuochi et al.: "The Structure and Electronic State of Photoexcited Fullerene Linked to a Nitroxide Radical Studied by an Analysis of a 2D Electron Paramagnetic Resonance Nutation Spectrum,"J. Chem. Phys.. 111. 3479-3484 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Mizuochi et al.: "First Observation of the Photoexcited Quintet State in Fullerene Linked with Two Nitroxide Radicals"Phys. Chem. A.. 103. 7749-7752 (1999)

    • Related Report
      1999 Annual Research Report

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

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