Grant-in-Aid for Scientific Research (A)
|Research Institution||Nagoya University|
FUNAHASI Shigenobu Nagoya University, Faculty of Science, Professor, 大学院・理学研究科, 教授 (30022700)
田口 武慶 (株)理学電機, 設計部, 研究員
長村 俊彦 (株)ユニソク, 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)
NAGAMURA Toshihiko Unisoku Co., Senior Researcher
TAGUCHI Takeyoshi Rigaku Co., Researcher
|Project Fiscal Year
1995 – 1996
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)
|Keywords||Reaction Intermediate / Short-Lived Species / EXAFS / Imaging Plate / Stopped-Flow Technique / Time-Resolved / Kinetic Analysis / 動態分析 / 反応中間体 / 短寿命化学種 / EXAFS法 / イメージングプレート / ストップトフロー法 / エネルギー分散型 / 時間分解 / ストップフロー法|
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
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