Molecular mechanism of liquid-liquid interfacial complexation and development of its function

本研究的目的是发明新的液液界面单分子行为和金属络合动力学的测量方法，并阐明界面的纳米性质和络合反应的动力学机理。得到了以下有用的结果：1)单分子探针法评价界面的纳米性质通过荧光显微镜观察到吸附在界面上的单一荧光分子。根据观测结果，首次对界面扩散系数和界面粘度进行了估算。研究了共吸附表面活性剂分子对单分子扩散的影响。2)界面反应直接测量法的发明离心液膜法在不同的溶剂萃取体系中的应用得到证实。为了测量高达几微秒的快速界面反应，建立了一种新型的微鞘流动荧光显微镜。3)界面催化和界面分子识别当配体或中间络合物在反应过程中发生吸附时，界面上的络合反应总是被催化的。这些发现对于考虑界面催化作用的溶剂萃取系统的设计是有用的。研究发现，金属络合物在界面处的聚集比在体相中的聚集更有利。4)界面的分子模拟成功地将分子模拟方法应用于配体的界面吸附能的估算。

The aim of this study was to invent new measurement methods of a single molecule behavior and metal complexation kinetics at the liquid-liquid interface and to elucidate the nano property of the interface and the kinetic reaction mechanisms of the complexation. Following useful results were obtained;1) Evaluation of nanoproperty of the interface by the single molecule probe methodA single fluorescent molecule adsorbed at the interface was chased by a fluorescent microscopy. From observed results, the diffusion coefficient at the interface and the viscosity of the interface was evaluated for the first time. The effect of co-adsorbed surfactant molecules on the single molecule diffusion was also evaluated.2) Invention of direct measurement method of interfacial reactionsThe utility of the centrifugal liquid membrane method was confirmed in various solvent extraction systems. To measure fast interfacial reaction as rapid as a few micro second, a new micro-sheath flow fluorescence microscopy was constructed. Furthermore, a centrifugal liquid membrane/ Raman microscopy and a micro-two phase mass spectrometry were invented.3) Interfacial catalysis and molecular recognition at the interfaceComplexation at the interface was always catalyzed when the adsorption of the ligand or the intermediate complex took place in the process of the reaction. These findings are useful for the design of solvent extraction systems taking into account the catalytic role of the interface. We find out that the aggregation of metal complex was favored at the interface than in bulk phase. Also, the interfacial aggregation exhibited novel molecular recognition ability for nucletic acid bases and diazine isomers.4) Molecular simulation of the interfaceMolecular simulation method was successfully applied for the estimation of the interfacial adsorption energy of ligand.