1990 Fiscal Year Annual Research Report

固相反応における動的過程の解析

Research Project

Project/Area Number	02210105
Research Institution	The Institute of Physical and Chemical Research
Principal Investigator	岩崎準理化学研究所, 結晶学研究室, 主任研究員 (20087399)
Co-Investigator(Kenkyū-buntansha)	伊藤正時慶応大学, 理工学部, 教授 (80005438) 小林隆史京都大学, 教授 (50027059) 田中勲北海道大学, 理学部, 助教授 (70093052) 大胡恵明新潟薬科大学, 薬学部, 教授 (10016115) 大橋裕二東京工業大学, 理学部, 教授 (40016118)
Keywords	分子性結晶 / 固相反応 / 結晶相反応 / 動的解析 / 迅速X線測定 / 電子顕微鏡 / 反応過程 / 結晶成長
Research Abstract	固相化学反応の動的過程を原子レベルで定量的に解明するために,反応途中の各段階における結晶構造の変化を追跡することがきわめて重要であるとの観点から,1時間以内で構造解析に必要な単結晶X線回折デ-タ測定を完了することを目指した新しい実験室系の迅速X線カメラ系を開発した。平成元年度のハ-ド部分及び基本ソフトの開発整備に引続いて,本年度は光学系・デ-タ記録系・ソフトウェアを改良し,装置を完成させた。またイメ-ジングプレ-トの詳細な特性評価を行った。光学活性コバロキシム錯体の固相・結晶相ラセミ化反応やβ→α異性化反応については,種々の新しい反応系を見いだすと共に,多数の結晶構造をX線解析により明らかにし,反応速度と置換基の立体構造や結晶内反応空間との関係を系統的に議論した。また時間分割の動的X線解析により,結晶相ラセミ化反応の途中段階にある分子の準安定構造を捕えることに初めて成功した。さらに結晶基盤上での有機金属分子の反応,導電性LB膜の光照射による異性化反応,有機電荷移動錯体のエピタクシアル成長,金属錯体結晶中の光励起緩和,固体水素結晶等における水素の結合組替えトンネル反応など,種々の固相反応あるいは結晶表面の関わる有機化学反応について,それぞれの動的過程をX線回折・高分解能電子顕微鏡観察・高速電子線エネルギ-損失分光。フ-リエ変換赤外分光。表面ラマン分光・表面偏光EXAFS・ペニングイオン化電子分光・電子スピン共鳴などのさまざまな物理化学的手法により研究し,固相・表面相の化学反応について多大の知見を得ることができた。また,これらの研究を可能とするため,各種分光法に関係した装置の開発・改良を進めた。

Research Products

(19 results)

All Other

All Publications (19 results)

[Publications] Y.Sngawara,N.Kamiya,H.Iwasaki,T.Ito,Y.Satow: "Humidity Induced Reversible Transition between Na_2 ATP Dihydrate and Trihydrate Coupling with Conformational Change of ATP" J.Am.Chem.Soc.,in press.(1991)
[Publications] H.Iwasaki: "Design of a Laboratory XーRay Measurement System for TimeーResolved Structural Study" Proc.12th Seminar on Sci.and Techn.ーCrystalーliography,Interchange Association,Tokyo. 145-151 (1991)
[Publications] Y.Ohashi,A.Sekine,E.Shimizu,K.Hori,A.Uchida: "Three Factors Controlling the Reaction Rate in Solid State Photoisomerization" Mol.Cryst.Liq.Cryst.186. 37-44 (1990)
[Publications] Y.Mori,K.Maeda,Y.Ohashi: "Structures and the Photochemical HydrogenーAbstraction Reaction of Tetraー1.5ーpentanediones" Acta Cryst.B46. 665-671 (1990)
[Publications] I.Fujii,N.Yasuoka: "Evaluation of XーRay Diffraction Data from Protein Crystals by use of an Imaging Plate" Acta Cryst.B47. (1991)
[Publications] T.Kobayashi,N.Asaka,T.Maeda,N.Kawase: "Defect Structures of Organic Thin Crystals Studied by Direct Imaging of Molecules with High Resolution Electron Microscope" Defect Control in Semiconductors. 1. 1623-1627 (1990)
[Publications] S.Masuda: "Penning Ionization Electron Spectroscopy of TetraーfluoroーTCNQ Anion without CounterーIon Prepared on Graphite" Chem.Phys Lett.(1991)
[Publications] S.Masuda: "Spatial Distribution of Wave Function of a Graphite Surface Studied by use of MetastableーAtom Electron Spectroscopy" Phys Rev.B42. 3582-3585 (1990)
[Publications] T.Miyazaki,N.Iwata,K.Fueki,H.Hase: "Observation of ESR Spin Flip Satellite Lines of Trapped H Atoms in Solid H_2 at 4.2K" J.Phys.Chem.94. 1702-1705 (1990)
[Publications] T.Miyazaki,T.Hiraku,K.Fueki,Y.Tsuchihashi: "Effect of Rotational Quantum States (S=0.1) on the Tunneling Reaction H_2+H→H+H_2 in para H_2 Solid at 4.2K" J.Phys.Chem.95. 26-29 (1991)
[Publications] 浅野素子,海津洋行: "金属ポルフィリン錯体の光励起緩和過程" 分光研究. 39. 149-163 (1990)
[Publications] H.Kimura,Y.Kaizu,H.Kobayashi: "Magnetic Circular Dichroism in the ChargeーTransferーtoーSolvent Excited States of Iodide Ion in Aqueous Solution" Mol.Phys.70. 891-902 (1990)
[Publications] J.Jeszka,A.Tracz,J.Ulanski,J.Kobayashi et al.: "Submicroscopic Structure of the TTFーTCNQ Conductive Network in RectilatedーDoped Polymers Revealed by SEM" Synthetic Metals. 35. 215-220 (1990)
[Publications] M.Takahashi,H.Idetsuki,M.Ito: "SERS of Benzere on a Silver Electrode:The Effect of Electrode Potential and Electrolyte Anions" Surface Sci.232. 346-352 (1990)
[Publications] S.Watanabe,Y.Kinomoto,F.Kitamura,M.Takahashi,M.Ito: "An Infrared Study of CO Adsorbed on Pt(100)and Pt(110) Electrodes:Dynamic Aspects of CO at Reconstructed Surfaces" J.Electron Spectrosc.and Related Phen.54/55. 1205-1214 (1990)
[Publications] X.ーZ.Wu,T.Kitamori,N.Teramae,T.Sawada: "Depth Profiling Using Fluorescence Spectroscopy Based on Reciprocal Principle" Bull.Chem.Soc.Jpn.64. (1991)
[Publications] K.Asakura,K.Bando,Y.Iwasawa,et al: "MetalーAssisted Hydroformylation on a StO_2ーAttached Rh Dimer.Inーsitu EXAFS and FTーIR Observations of the Dynamic Behavior of the Dimer Site" J.Am.Chem.Soc.112. 9096-9104 (1990)
[Publications] K.Asakura,Y.Iwasawa: "Characterization of Nb Monolayer Catalyst by means of EXAFS" Conf.Proc.SIF,Bologna. 25. 513-516 (1990)
[Publications] T.Kobayashi: "Crystals/Growth,Properties and Applications Vol.13 Organic Crystals I:Characterization.Ed.N.Karl." SpringerーVerlag.Berlin Heidelberg, 91-161 (1991)

1990 Fiscal Year Annual Research Report

固相反応における動的過程の解析

Principal Investigator

岩崎 準 理化学研究所, 結晶学研究室, 主任研究員 (20087399)

Research Products

[Publications] Y.Sngawara,N.Kamiya,H.Iwasaki,T.Ito,Y.Satow: "Humidity Induced Reversible Transition between Na_2 ATP Dihydrate and Trihydrate Coupling with Conformational Change of ATP" J.Am.Chem.Soc.,in press.(1991)

[Publications] H.Iwasaki: "Design of a Laboratory XーRay Measurement System for TimeーResolved Structural Study" Proc.12th Seminar on Sci.and Techn.ーCrystalーliography,Interchange Association,Tokyo. 145-151 (1991)

[Publications] Y.Ohashi,A.Sekine,E.Shimizu,K.Hori,A.Uchida: "Three Factors Controlling the Reaction Rate in Solid State Photoisomerization" Mol.Cryst.Liq.Cryst.186. 37-44 (1990)

[Publications] Y.Mori,K.Maeda,Y.Ohashi: "Structures and the Photochemical HydrogenーAbstraction Reaction of Tetraー1.5ーpentanediones" Acta Cryst.B46. 665-671 (1990)

[Publications] I.Fujii,N.Yasuoka: "Evaluation of XーRay Diffraction Data from Protein Crystals by use of an Imaging Plate" Acta Cryst.B47. (1991)

[Publications] T.Kobayashi,N.Asaka,T.Maeda,N.Kawase: "Defect Structures of Organic Thin Crystals Studied by Direct Imaging of Molecules with High Resolution Electron Microscope" Defect Control in Semiconductors. 1. 1623-1627 (1990)

[Publications] S.Masuda: "Penning Ionization Electron Spectroscopy of TetraーfluoroーTCNQ Anion without CounterーIon Prepared on Graphite" Chem.Phys Lett.(1991)

[Publications] S.Masuda: "Spatial Distribution of Wave Function of a Graphite Surface Studied by use of MetastableーAtom Electron Spectroscopy" Phys Rev.B42. 3582-3585 (1990)

[Publications] T.Miyazaki,N.Iwata,K.Fueki,H.Hase: "Observation of ESR Spin Flip Satellite Lines of Trapped H Atoms in Solid H_2 at 4.2K" J.Phys.Chem.94. 1702-1705 (1990)

[Publications] T.Miyazaki,T.Hiraku,K.Fueki,Y.Tsuchihashi: "Effect of Rotational Quantum States (S=0.1) on the Tunneling Reaction H_2+H→H+H_2 in para H_2 Solid at 4.2K" J.Phys.Chem.95. 26-29 (1991)

[Publications] 浅野 素子,海津 洋行: "金属ポルフィリン錯体の光励起緩和過程" 分光研究. 39. 149-163 (1990)

[Publications] H.Kimura,Y.Kaizu,H.Kobayashi: "Magnetic Circular Dichroism in the ChargeーTransferーtoーSolvent Excited States of Iodide Ion in Aqueous Solution" Mol.Phys.70. 891-902 (1990)

[Publications] J.Jeszka,A.Tracz,J.Ulanski,J.Kobayashi et al.: "Submicroscopic Structure of the TTFーTCNQ Conductive Network in RectilatedーDoped Polymers Revealed by SEM" Synthetic Metals. 35. 215-220 (1990)

[Publications] M.Takahashi,H.Idetsuki,M.Ito: "SERS of Benzere on a Silver Electrode:The Effect of Electrode Potential and Electrolyte Anions" Surface Sci.232. 346-352 (1990)

[Publications] S.Watanabe,Y.Kinomoto,F.Kitamura,M.Takahashi,M.Ito: "An Infrared Study of CO Adsorbed on Pt(100)and Pt(110) Electrodes:Dynamic Aspects of CO at Reconstructed Surfaces" J.Electron Spectrosc.and Related Phen.54/55. 1205-1214 (1990)

[Publications] X.ーZ.Wu,T.Kitamori,N.Teramae,T.Sawada: "Depth Profiling Using Fluorescence Spectroscopy Based on Reciprocal Principle" Bull.Chem.Soc.Jpn.64. (1991)

[Publications] K.Asakura,K.Bando,Y.Iwasawa,et al: "MetalーAssisted Hydroformylation on a StO_2ーAttached Rh Dimer.Inーsitu EXAFS and FTーIR Observations of the Dynamic Behavior of the Dimer Site" J.Am.Chem.Soc.112. 9096-9104 (1990)

[Publications] K.Asakura,Y.Iwasawa: "Characterization of Nb Monolayer Catalyst by means of EXAFS" Conf.Proc.SIF,Bologna. 25. 513-516 (1990)

[Publications] T.Kobayashi: "Crystals/Growth,Properties and Applications Vol.13 Organic Crystals I:Characterization.Ed.N.Karl." SpringerーVerlag.Berlin Heidelberg, 91-161 (1991)

岩崎準理化学研究所, 結晶学研究室, 主任研究員 (20087399)

[Publications] 浅野素子,海津洋行: "金属ポルフィリン錯体の光励起緩和過程" 分光研究. 39. 149-163 (1990)