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

使用成像板探测器开发高分辨率实验室快速 EXAFS 设备

• 批准号: 07504003
• 负责人: FUNAHASI Shigenobu
• 金额: $ 26.5万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07504003/
• 关键词: Reaction 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

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 DetectorThe 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 RadiationOn 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 SystemsThe 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

动态反应过程中各物质每时每刻都在变化和反应，关键物质的检测对分子水平的分析具有重要意义。由于反应中间体和短寿命物质的动态行为的检测和评价是动态反应系统分析的关键，我们在本工作中进行了以下研究1。使用成像板检测器的停流实验室EXAFS装置的研制停流实验室EXAFS装置由一个以薄板Ge（111）晶体作为色散模式多色仪的测角仪、一个快速成像板检测器和一个停流样品混合装置组成。成像板绕着旋转的dram旋转，并暴露在通过停流组件中的样品单元的透射x射线下。利用同步辐射研制时间分辨停止流EXAFS系统在实验室EXAFS装置研制的基础上，在高能物理国家实验室光子工厂BL-12C站研制了同步辐射时间分辨停止流EXAFS系统。该系统由作为x射线探测器的电离室、快速电流放大器、适合BL-12C的停止流动样品混合装置和用于步进扫描法中时间分辨测量的快速a /D转换器组成。由于离子在电离室中的漂移速度，其最小时间分辨率约为1 ms，所用止流装置的死区时间为3.6 ms。在某些快速反应体系动力学分析中的应用利用两台新研制的时间分辨EXAFS仪器对以下反应体系中的反应中间体进行了结构测定，并对反应机理进行了评价。(1) [Fe (CN) _6] ^<3->与_l -抗坏血酸的氧化还原反应(2)Fe^<2+>与[Co (NH_3) _5Cl] ^<2+>在N，N-二甲基甲酰胺中的氧化还原反应(3)金属卟啉在乙腈中形成5,10,15,20-四苯基卟啉

项目成果

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)

S. Aizawa 和 S. Funahashi：“通过三方双锥钯 (II) 配合物与三（2-二苯基膦乙基）膦的 31 PNMR 化学位移表征溶剂的 σ 和 π 供给”，《分析科学》12。27-。 30 (1996)

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" In

S.Aizawa 等人：“三（2-（二苯基膦基）乙基）膦与亚磷酸三甲酯在氯仿中在不同温度和压力下五配位三方双锥钯（II）配合物卤代配体取代的机理研究”

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).

S. Aizawa 等人：“通过 31PNMR 化学位移表征溶剂的 σ 和 π 供体，三方双锥钯 (II) 配合物与三(2-二苯基膦乙基)phpsphine”分析科学（正在出版）。

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)

船桥重信：“无机化学的详细解释”讲谈社科学，20（1996）

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 Cadmium (II) Ions in Aqueous Solution at Various Temepratures and Pressures. Effects

M.Inamo 等人：“5,10,15,20-四（4-磺基-苯基）卟啉及其-N-甲基化衍生物与锌 (II) 和镉 (II) 离子络合的热力学和动力学研究