Clarification of Dynamic Behavior of Metal Ions in Solution and Development of Dynamic Analytical Chemistry

溶液中金属离子动态行为的澄清和动态分析化学的发展

基本信息

  • 批准号:
    10440221
  • 负责人:
  • 金额:
    $ 7.3万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (B).
  • 财政年份:
    1998
  • 资助国家:
    日本
  • 起止时间:
    1998 至 2000
  • 项目状态:
    已结题

项目摘要

We can expect the enhancement of the selectivity and sensitivity in analysis by introducing the axis of time. We believe that a key point of the clarification of the mechanisms and reactivities of the reactions in solution is to detect and analyze the reaction intermediates and transition states. Our purpose is to develop the so-called dynamic Analytical Chemistry. We systematically pursued the mechanistic study on the reactions concerning metal ions in solution for Analytical Chemistry.(1) The relation between the solvation structures of metal ions and their reactivities has been clarified based on the following results : (a) the solvation structures of metal ions determined by EXAFS technique, (b) the kinetics and mechanism of the solvent exchange determined by NMR technique, and (c) the transition states of the water exchange on the transition metal (II) ions evaluated by the ab initio molecular orbital method.(2) The solvent, chelate, and pressure effects for the formation of the m … More etal complexes of ligands with stereochemical character have been clarified based on the following mechanisms : (a) the mechanism for the formation and deprotonation of the sitting-atop complexes, (b) the mechanism for the metal ion incorporation of the polyol complexes of boric acid, (c) the cyclopalladation mechanism, and (d) the mechanism for complexation of beryllium (II) ion in non-aqueous solution.(3) The outer-sphere electron transfer reactions between metal (II/III) complexes have been systematically investigated where the structural rearrangement in the inner-sphere is the rate-determining step, and the so-called gated mechanism has been clarified in detail.(4) We pursued the methodology for dynamic analytical chemistry. Detection and analysis of the unstable reaction intermediates produced during reactions have been performed. We developed a time-resolved stopped-flow EXAFS instrument, a spectrophotometric cell and a stopped-flow apparatus for supercritical carbon dioxide, and a high-frequency resonance spectrometer. Less
我们可以通过引入时间轴来期望分析中选择性和灵敏度的提高。我们认为,溶液中反应的机理和反应性的关键是检测和分析反应中间体和过渡状态。我们的目的是开发所谓的动态分析化学。 We systematically pursued the mechanical study on the reactions concerning metal ions in solution for Analytical Chemistry.(1) The relationship Between the solution structures of metal ions and their reactivities has been clarified based on the following results: (a) the solution structures of metal ions determined by EXAFS technology, (b) the kinetics and mechanism of the solvency exchange determined by NMR technology, and (c) the transition states of the water exchange on the transition metal (ii)通过从头算分子轨道方法评估的离子。(2)基于以下机制,已经阐明了具有立体化学特征的M…更耐心的配体的溶液,珍贵和压力效应:(a)用于坐姿的机制,用于坐姿的机制(a)坐姿的机制,用于坐姿的机制,(B)拟合物的机制,(B)bolotion的机制(B)bolotion的机制,(B) (c)在非水溶液中凝聚碱离子络合(II)离子的机制。(3)金属(II/III)络合物之间的外球电子转移反应已被系统地研究了,该反应已在速率上进行了速率(四个详细的速度),在其中的结构重排是在该机构中的结构重排,该机构已定义了(详细介绍的机制)(又是详细的(So-nection)。动态分析化学方法的方法。已经对反应过程中产生的不稳定反应中间体进行了检测和分析。我们开发了一种时间分辨的停止流量EXAFS仪器,一个分光光度计电池和一个用于超临界二氧化碳的止流仪,以及高频共振光谱仪。较少的

项目成果

期刊论文数量(226)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
舟橋 重信: "無機溶液反応の化学" 裳華房, 271 (1998)
Shigenobu Funahashi:“无机溶液反应的化学” Shokabo,271(1998)
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    0
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  • 通讯作者:
T.Yagyu,S.Iwatsuki,S.Aizawa,and S.Funahashi: "Electronic Effect of Substitutes on Cyclopalladation of the Solvated Palladium (II) Complexes with N-Benzyl Triamine [Pd (Sol) {(4-XC_6H_4CH_2)_3NH (CH_2)_3NR (CH_2)_3NH_2}]^<2+> (Sol=Solvent ; R=Ph, H, and Me
T.Yagyu、S.Iwatsuki、S.Aizawa 和 S.Funahashi:“取代基对溶剂化钯 (II) 配合物与 N-苄基三胺 [Pd (Sol) {(4-XC_6H_4CH_2)_3NH 环钯化的电子效应”
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    0
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N.Koshino,Y.Kuchiyama,H.Ozaki,S.Funahashi,and H.D.Takagi: "An Interpretation of Gated Behavior : Kinetic Studies of the Oxidation and Reduction Reactions of Bis (2,9-dimethyl-1,10-phenanthroline) copper (I/II) in Acetonitrile"Inorganic Chemistry. 38・14. 3
N.Koshino、Y.Kuchiyama、H.Ozaki、S.Funahashi 和 H.D.Takagi:“门控行为的解释:双(2,9-二甲基-1,10-菲咯啉)氧化和还原反应的动力学研究乙腈中的铜(I/II)”无机化学.38・14.3
  • DOI:
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  • 影响因子:
    0
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  • 通讯作者:
Y.Inada,Y.Nakano,M.Inamo,M.Nomura,and S.Funahashi: "Structural Characterization and Formation Mechanism of Sitting-Atop (SAT) Complexes of 5,10,15,20-Tetraphenylporphyrin with Divalent Metal Ions.Structure of the Cu(II)-SAT Complex As Determined by Fluore
Y.Inada、Y.Nakano、M.Inamo、M.Nomura 和 S.Funahashi:“5,10,15,20-四苯基卟啉与二价金属离子的坐顶 (SAT) 配合物的结构表征和形成机制。
  • DOI:
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  • 影响因子:
    0
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Y.Tsutsui, H.Wasada, and S.Funahashi: "Reaction Mechanism of Water Exchange on Di- and Trivalent Cations of the First Transition Series and Structural Stability of Seven-Coordinate Species"Journal of Molecular Structure (Theoretical Chemistry). 461-462. 3
Y.Tsutsui、H.Wasada 和 S.Funahashi:“第一过渡系列二价和三价阳离子的水交换反应机理和七配位物种的结构稳定性”分子结构杂志(理论化学)。
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    0
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FUNAHASHI Shigenobu其他文献

FUNAHASHI Shigenobu的其他文献

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{{ truncateString('FUNAHASHI Shigenobu', 18)}}的其他基金

Development of Observation System for Characterization in Supercritical Carbon Dioxide
超临界二氧化碳表征观测系统的开发
  • 批准号:
    11354009
  • 财政年份:
    1999
  • 资助金额:
    $ 7.3万
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
Speciation of Organotin (IV) Compounds and Evaluation of Light-Induced Decomposition Reaction
有机锡 (IV) 化合物的形态及光诱导分解反应的评价
  • 批准号:
    07454199
  • 财政年份:
    1995
  • 资助金额:
    $ 7.3万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Mechanistic Study of Metal Complex Formation and Its Application to Kinetic Analysis
金属配合物形成机理研究及其在动力学分析中的应用
  • 批准号:
    04403011
  • 财政年份:
    1992
  • 资助金额:
    $ 7.3万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (A)
Pressure effect of metal complex formation
金属配合物形成的压力效应
  • 批准号:
    62470041
  • 财政年份:
    1987
  • 资助金额:
    $ 7.3万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)

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Analytical chemistry studies on dynamic analyses of stable isotope analysis towards the isotopomics research foundation
稳定同位素动态分析的分析化学研究为同位素组学研究奠定基础
  • 批准号:
    23615006
  • 财政年份:
    2011
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