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Development of High-Resolution Laboratory Rapid EXAFS Apparatus Using an Imaging Plate Detector

Research Project

Project/Area Number 07504003
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section試験
Research Field 分離・精製・検出法
Research InstitutionNagoya University

Principal Investigator

FUNAHASI Shigenobu  Nagoya University, Faculty of Science, Professor, 大学院・理学研究科, 教授 (30022700)

Co-Investigator(Kenkyū-buntansha) TAGUCHI Takeyoshi  Rigaku Co., Researcher, 設計部, 研究員
NAGAMURA Toshihiko  Unisoku Co., Senior Researcher, 科学機器開発研究所, 主任研究員
INADA Yasuhiro  Nagoya University, Faculty of Science, Research Associate, 大学院・理学研究科, 助手 (60242814)
TAKAGI Hideo  Nagoya University, Faculty of Science, Associate Professor, 大学院・理学研究科, 助教授 (70242807)
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥41,400,000 (Direct Cost: ¥41,400,000)
Fiscal Year 1996: ¥8,400,000 (Direct Cost: ¥8,400,000)
Fiscal Year 1995: ¥33,000,000 (Direct Cost: ¥33,000,000)
KeywordsReaction Intermediate / Short-Lived Species / EXAFS / Imaging Plate / Stopped-Flow Technique / Time-Resolved / Kinetic Analysis / 時間分解 / ストップフロー法
Research Abstract

The detection of key species in dynamic reaction processes, in which the species change and react in every moment, is quite important for analysis in the molecular level. Because the detection and the evaluation of the dynamic behavior of reaction intermediates and short-lived species are the key points for the analysis in dynamic reaction systems, we have performed the following investigations in this work.
1.Development of Stopped-Flow Laboratory EXAFS Apparatus Using an Imaging Plate Detector
The stopped-flow laboratory EXAFS apparatus consists of a goniometer with a thin plate Ge (111) crystal as a polychromator in the dispersive mode, a fast imaging plate detector, and a stopped-flow sample-mixing apparatus. The imaging plate is rolled around a rotating dram and is exposed to transmitted X-rays through a sample cell in the stopped-flow assembly.
2.Development of Time-Resolved Stopped-Flow EXAFS System Using Synchrotron Radiation
On the basis of knowledges obtained in the development o … More f the laboratory EXAFS apparatus, the time resolved stopped-flow EXAFS system using synchrotron radiation has been developed at the BL-12C station of the Photon Factory of the National Laboratory for High Energy Physics. The system consists of ionization chambers as an X-ray detector, fast current amplifiers, the stopped-flow sample-mixing apparatus modified to fit BL-12C,and a fast A/D converter used for the time-resolved mesurement in the step-scanning method. The minimum time-resolution was on the order of 1 ms due to the drift velocity of ions in the ionization chamber, and the dead time was 3.6 ms for the used stopped-flow assembly.
3.Application to Dynamic Analysis for Some Fast Reaction Systems
The structural determination has been performed for the reaction intermediates in the following reaction systems by using two newly developed time-resolved EXAFS apparatus, and then the reaction mechanisms have been evaluated.
(1) Redox reaction between [Fe (CN) _6] ^<3-> and _L-ascorbic acid
(2) Redox reaction between Fe^<2+> and [Co (NH_3) _5Cl] ^<2+> in N,N-dimethylformamide
(3) Metalloporphyrin formation of 5,10,15,20-tetraphenylporphyrin in acetonitrile Less

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (46 results)

All Other

All Publications (46 results)

  • [Publications] S.Kagawa et al.: "Kinetic Study on Complexation of Boric Acid with 4-Isopropyltropolone in Nonaqueous Solvents" Inorganica Chimica Acta. 231. 115-119 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa et al.: "Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt (II), Iron (II), and Manganese (II) Ions in Ethylenediamine. Kinetic Chelate Effect and Chelate Strain Effect" Inorganic Chemistry. 34. 2042-2047 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Inamo et al.: "Reactivities of Five-Coordinate Intermediate Generated by Laser Photolysis of Monoligated Chloro (5,10,15,20-tetraphenylporphinato) chromium (III) in Toluene" Bulletin of the Chemical Society of Japan. 68. 2293-2303 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.D.Takagi et al.: "Mechanistic Study of Oxidation reaction of Hydroquinone Catecol, and L-Ascorbic Acid by Dicyanobis (1,10-phenanthroline) iron (III) in Dimethyl Sulfoxide" Journal of Molecular Liquids. 65/66. 277-280 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa et al.: "Crystal Struclures of Trifluoromethanesulfonato Complexes of Nickel (II) and Palladium (II), [Ni(bpy)_2(CF_3SO_3)_2]and [Pd(triphosphine)(CF_3SO_3)](CF_3SO_3)・C_6H_6, and Characterization of Coordination Ability of CF_3SO_3" Analytical Science. 11. 557-562 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa and S.Funahashi: "Characterization of σ and π Donation of Solvents by ^<31> PNMR Chemical Shifts of Trigonal-Bipyramidal Palladium (II) Complexes with Tris (2-diphenylphosphinoethyl) phosphine" Analytical Science. 12. 27-30 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 舟橋重信: "詳説無機化学" 講談社サイエンテイフイック, 20 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 舟橋重信: "無機溶液反応の化学" 裳華房 (in press),

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kagawa et al.: "Kinetic Study on Complexation of Boric Acid with 4-Isopropyltropolone in Nonaqueous Solvents" Inorganica Chimica Acta. 231. 115-119 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa et al.: "Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt (II), Iron (II), and Manganese (II) Ions in Ethylenediamine. Kinetic Chelate Effect and Chelate Strain Effect" Inorganic Chemistry. 34. 2042-2047 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Inamo et al.: "Reactivities of Five-Coordinate Intermediate Generated by Laser Photolysis of Monoligated Chloro (5,10,15,20-tetraphenylporphinato) -chromium (III) in Toluene" Bulletin of the Chemical Society of Japan. 68. 2293-2303 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.D.Takagi et al.: "Mechanistic Study of Oxidation Reaction of Hydroquinone, Catecol, and L-Ascorbic Acid by Dicyanobis (1,10-phenanthroline) iron (III) in Dimethyl Sulfoxide" Journal of Molecular Liquids. 65/66. 277-280 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa et al.: "Crystal Structures of Trifluoromethanesulfonato Complexes of Nickel (II) and Palladium (II) and Palladium (II), [Ni (bpy) _2 (CF_3SO_3) _2] and [Pd (triphosphine) (CF_3SO_3)] (CF_3SO_3)・C_6H_6, and Characterization of Coordination Ability of CF_3SO_3^-" Analytical Science. 11. 557-562 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa and S.Funahashi: "Characterization of sigma and pi Donation of Solvents by ^<31>P NMR Chemical Shifts of Trigonal-Bipyramidal Palladium (II) Complexes with Tris (2-diphenylphosphinoethyl) phosphine" Analytical Science. 12. 27-30 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa et al.: "Nitrogen-14 NMR Study on Solvent Exchange of Octahedral Cobalt (II) Ion in Neat 1,3-Propanediamine and n-Propylamine at Various Temperatures and Pressures. Tetrahedral-Octahedral Equilibrium of Solvated Cobalt (II) Ion in n-Propylamine As Studied by EXAFS and Electronic Absorption Spectroscopy" Inorganic Chemistry. 35. 1338-1342 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa et al.: "Complexation Equilibria and Structures of Dimethyltin (IV) Complexes with N-Methylimino-diacetate, Pyridine-2,6-dicarboxylate, Ethylenediamine-N,N'-diacetate, and Ethylenediamine-N,N,N', N'-tetraacetate" Inorganica Chimica Acta. 248. 215-224 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Yagyu et al.: "Crystal Structures and Acetonitrile Exchange of Palladium (II) Complexes with Bis (3-amino-propyl) amine and Diethyltriamine. Effects of Ion-Pair Formation" Bulletin of the Chemical Society of Japan. 69. 1961-1967 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa et al.: "Mechanistic Studies on Halo-Ligand Substitution of Five-Coordinate Trigonal-Bipyramidal Palladium (II) Complexes of Tris (2- (diphenylphosphino) ethyl) phosphin with Trimethyl Phosphite in Chloroform at Various Temperatures and Pressures" Inorganic Chemistry. 35. 5163-5167 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Inada et al.: "Spectral Evidence and Kinetics for Formation of the Sitting-Atop Complex of Copper (II) Ion with 5,10,15,20-Tetraphenylporphyrin in Acetonitrile" Chemistry Letters. 881-882 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Yagyu et al.: "Kinetics and Mechanism of Cyclopalladation for [Pd (S) (Bn_2Me dptn)] (BF_4) _2 (S=Solvent, Bn_2Medptn=N,N''-Dibenzyl-N'-methyl-3,3'-diaminodipropylamine) and Its Derivatives" Chemistry Letters. 1107-1108 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Matsumoto et al.: "Oxidation Reaction of L-Ascorbic Acid by Dicyanobis (1,10-phenenthroline) iron (III) in Dimethyl Sulfoxide at Elevated Pressures.Evidence for the Adiabatic Electron Transfer" Inorganica Chimica Acta. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Inamo et al.: "Thermodynamic and Kinetic Studies on Complexation of 5,10,15,20-Tetrakis (4-sulfonato-phenyl) porphine and Its N-Methylated Derivative with Zinc (II) and Ca dmium (II) Ions in Aqueous Solution at Various Temepratures and Pressures.Effects of Metal Ion Size and Porphine Ring Deformation on Metal-Ion Incorporation to Porphyrins" Inorganica Chimica Acta. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Aizawa and S.Funahashi: "Characterization of σ and π Donation of Solvents by ^<31>P NMR Chemical Shifts of Trigonal-Bipyramidal Palladium(II) Complexes with Tris(2-diphenylphosphinoethyl)phosphine" Analytical Science. 12. 27-30 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Aizawa et al.: "Nitrogen-14 NMR Study on Solvent Exchange of Octahedral Cobalt(II) Ion in Neat 1.3-Propanediamine and n-Propylamine at Various Temperatures and Pressures. Tetrahedral-Octahedral Equilibrium of Solvated Cobalt(II) Ion in n-Propylamine As Studied by EXAFS and Electronic Absorption Spectroscopy" Inorganic Chemistry. 35. 1338-1342 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Aizawa et al.: "Complexation Equilibria and Structures of Dimethyltin(IV) Complexes with N-Methylimino-diacetate,Pyridine-2,6-dicarboxylate,Ethylenedi-amine-N,N-diacetate,and Ethylenediamine-N<N<N<N-tetraacetate" Inorganica Chimica Acta. 248. 215-224 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Yagyu et al.: "Crystal Structures and Acetonitrile Exchange of Palladium(II) Complexes with Bis(3-amino-propyl)amine and Diethyltriamine. Effects of Ion-Pair Formation" Bulletin of the Chemical Society of Japan. 69. 1961-1967 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Aizawa et al.: "Mechanistic Studies on Halo-Ligand Substitution of Five-Coordinate Trigonal-Bipyramidal Palladium(II) Complexes of Tris(2-(diphenylphosphino)ethyl)phosphine with Trimethyl Phosphite in Chloroform at Various Temperatures and Pressures" Inorganic Chemistry. 35. 5163-5167 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Inada et al.: "Spectral Evidence and Kinetics for Formation of the Sitting-Atop Complex of Copper(II) Ion with 5,10,15,20-Tetraphenylporphyrin in Acetonitrile" Chemistry Letters. 881-882 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Yagyu et al.: "Kinetics and Mechanism of Cyclopalladation for [Pd(S)(Bn_2Me dptn)](BF_4)_2 (S=Solvent,Bn_2 Medtn=N,N^<11>-Dibenzyl-N^1-methyl-3,3'-diaminodipropylamine) and Its Derivatives" Chemistry Letters. 1107-1108 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Matsumoto et al.: "Oxidation Reaction of L-Ascorbic Acid by Dicyanobis(1,10-phenenthroline)iron(III) in Dimethyl Sulfoxide at Elevated Pressures. Evidence for the Adiabatic Electron Transfer" Inorganica Chimica Acta. (in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Inamo et al.: "Equilibria,Kinetics,and Mechanism of Complexation of 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphine and Its N-Methylated Derivative with Cadmium(II) and Zinc(II) Ions in Aqueous Solution at Variouos Temperatures and Pressures. Effects of Metal Ion Size and Porphyrin Ring Deformation on Metal Ion Incorporation" Inorganica Chimica Acta. (in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Tsutsui et al.: "EXAFS and Ab Initio Molecular Orbital Studies on the Structure of Solvated Silver(I) Ions" The Journal of Physical Chemistry. (in press).

    • Related Report
      1996 Annual Research Report
  • [Publications] 舟橋重信: "詳説 無機化学" 講談社サイエンティフィック, 20 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 舟橋重信: "無機溶液反応の化学" 裳華房(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Kagawa et al.: "Kinetic Study on Complexation of Boric Acid with 4-Isopropyltropolone in Nonaqueous Solvents" Inorganica Chimaca Acta. 231. 115-119 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Aizawa et al.: "Variable-Temperature and -Pressure Multinuclear Magnetic Resonance Studies on Solvent Exchange of Cobalt(II),Iron(II),and Manganese(II)Ions in Ethylenediamine.Kinetic Chelate Effect and Chelate Strain Effect" Inorganic Chemistry. 34. 2042-2047 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Inamo et al.: "Reactivities of Five-Coordinate Intermediate Generated by Laser Photolysis of Monoligated Chloro(5,10,15,20-tetraphenylporphinato)-chromium(III)in Toluene" Bulletin of the Chemical Society of Japan. 68. 2293-2303 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.D.Takagi et al.: "Mechanistic Study of Oxidation Reaction of Hydroquinone,Catechol,and L-Ascorbic Acid by Dicyanobis(1,10-phenanthroline)iron(III)in Dimethyl Sulfoxide" Journal of Molecular Liquids. 65/66. 277-280 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] P.D.Metelski et al.: "Electron Exchange Kinetics in a Tetrahedrally Coordinated Copper(II/I)Couple" Canadian Jounal of Chemistry. 73. 61-69 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Aizawa et al.: "Crystal Structures of Trifluoromethanesulfonato Complexes of Nickel(II)and Palladium(II),[Ni(bpy)_2(CF_3SO_3)_2]and[Pd(triphosphine)(CF_3SO_3)](CF_3SO_3)・C_6H_6,and Characterization of Coordination Ability of CF_3SO_3^-" Analytical Science. 11. 557-562 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Aizawa et al.: "Characterization of σ and π Donation of Solvents by ^<31>PNMR Chemical Shifts of Trigonal-Bipyramidal Palladium(II)Complexes with Tris(2-diphenylphosphinoethyl)phpsphine" Analytical Science. (in press).

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Aizawa et al.: "Nitrogen-14 NMR Study on Solvent Exchange of Octahedral Cobalt(II)Ion in Neat 1,3-Propanediamine and n-Propylamine at Various Temperatures and Pressures.Tetrahedral-Octahedral Equilibrium of Solvated Cobalt(II)Ion in n-Propylamine As Studied by EXAFS and Electronic Absorption Spectroscopy" Inorganic Chemistry. (in press).

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Matsumoto et al.: "Oxidation Reaction of L-Ascorbic Acid by Dicyanobis(1,10-phenanathroline)iron(III)in Dimethyl Sulfoxide at Elevated Pressures.Evidence for the Adiabatic Electron Transfer" Inorganica Chimica Acta. (in press).

    • Related Report
      1995 Annual Research Report
  • [Publications] H.D.Takagi et al.: "Estimation of the Outersphere Contribution to the Activation Volume for Electron Exchange Reactions by Using the Mean Spherical Approximation" Chemical Physics Letters. (in press).

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Aizawa et al.: "Complexation Equilibria and Structures of Dimethyltil(IV)Complexes with N-Methyliminodiacetate,Pyridine-2,6-dicarboxylate,Ethylenediamine-N,N'-diacetate,and Ethylenediamine-N,N,N',N'-tetraacetate" Inorganic Chemistry. (in press).

    • Related Report
      1995 Annual Research Report
  • [Publications] 舟橋重信: "詳説 無機化学" 講談社サイエンティフィック, 20 (1996)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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