Measurements and molecular dynamics simulations of complexation at liquid-liquid interfaces

液-液界面络合的测量和分子动力学模拟

• 批准号: 10440222
• 负责人: WATARAI Hitoshi
• 金额: $ 8.64万
• 依托单位: Osaka University
• 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 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10440222/
• 关键词: liquid-liquid interface; metal complexation; interfacial recognition reaction; interfacial relaxation; binuclear complex; high-speed stirring method; centrifugal liguid membrane method; molecular dynamics; 高速攪拌法; 界面反応速度; ポルフィリン; 界面吸着エネルギー; 分子動

1) Development of new methods for the measurements of fast complexation at the interfacesImproving the previous methods of a high-speed stirring method and a two-phase stopped flow method, we invented the new methods of a centrifugal liquid membrane method, a microscopic sheath flow method and a laser relaxation method for the measurement of rapid interfacial reaction.2) Elucidation of essential factors governing the interfacial reactionThe elemental processes of the interfacial complexation reaction were determined by the adsorptivity of a ligand, the solvation of the ligand and metal complex, the ligand substitution rate at the interface, the adsorptivity and reactivity of the intermediate complexes. In the present study, we determined between these factors and interfacial reaction rates in various reaction systems of transition metal ions with pyridylazo-ligands and in the demetalation or aggregation of metal-porphyrin.3)Evaluation of interfacial reactivity by the molecular dynamics simulationsStructures of the solvent molecules and the adsorbed ligand or complexes at the liquid-liquid interfaces were simulated in the systems of 2-hydroxyoxime in heptane/water system. Simulation over 1ns could demonstrate the adsorption behavior of the solute molecule of complex which tended to adsorb at the interface. Evaluation method of the adsorption energy was also developed.

1)界面快速络合测定新方法的研究改进了以往的高速搅拌法和两相停流法，提出了离心液膜法、显微鞘流法和激光弛豫法测定界面快速络合反应的新方法。2)阐明了影响界面快速络合反应的主要因素。在本研究中，我们确定了这些因素与过渡金属离子与吡啶偶氮配体的不同反应体系以及金属-卟啉的脱金属或聚集反应中的界面反应速率之间的关系。3)用分子动力学模拟方法评价界面反应活性。超过1 ns的模拟结果表明，络合物溶质分子的吸附行为倾向于吸附在界面上。并提出了吸附能的估算方法。

项目成果

H. Watarai and I. Takahashi: "Comparison of three different microemulsion systems as the run buffer for the capillary electrophoretic separation of ketone test solutes"Anal. Comunication. 35. 289-292 (1998)

H. Watarai 和 I. Takahashi：“作为酮测试溶质毛细管电泳分离运行缓冲液的三种不同微乳液系统的比较”

Hitoshi Watarai: "Interfacial adsorption and complexation in liquid-liquid extraction systems"Pure & Appl. Chem.. 70 (19). 1889-1893 (1998)

Hitoshi Watarai：“液-液萃取系统中的界面吸附和络合”Pure

A.Matsumoto: "Electrospray ionization mass spectrometry of metal complexes. Gas phase formation of a binuclear copper(II)-5-Br-PADAP complex"Anal. Chim. Acta. 390. 193-199 (1999)

A.Matsumoto：“金属络合物的电喷雾电离质谱。双核铜(II)-5-Br-PADAP络合物的气相形成”分析。

Y. Onoe, S. Tsukahara, and H. Watarai: "Central effect of N, N-dimethyl-4-(2-pyridylazo)aniline on the extraction rate of Ni(II) with 1-(2-pyridylazo)-2-naphthol : Ligand-substitution mechanism at the liquid-liquid interface"Bull. Chem. Soc. Jpn.. 71. 603

Y. Onoe、S. Tsukahara 和 H. Watarai：“N,N-二甲基-4-(2-吡啶基偶氮)苯胺对 1-(2-吡啶偶氮)-2 萃取 Ni(II) 率的中心效应

S. Tsukahara and H. Watarai: "Transient attanuated total internal reflection spectroscopy to measure the relaxation kinetics of triplet state of tetra(N-methylpyridinium-4-yl)porphine at liquid-liquid interface"Chem. Lett,. 89-90 (1999)

S. Tsukahara 和 H. Watarai：“瞬态衰减全内反射光谱法测量液-液界面四（N-甲基吡啶鎓-4-基）卟啉三重态的弛豫动力学”Chem。