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

本研究的目的是建立一种新的测量方法，在液-液界面上的单分子行为和金属络合动力学，并阐明界面的纳米性质和络合的动力学反应机理。获得了以下有益的结果：1）单分子探针法评价界面的纳米性质用荧光显微镜追踪吸附在界面上的单个荧光分子。从观测结果，在界面处的扩散系数和界面的粘度的评价第一次。2）界面反应直接测量方法的发明离心液膜法在各种溶剂萃取体系中的应用得到了证实。为了测量几微秒内的快速界面反应，构建了一种新的微鞘流荧光显微镜。3）界面催化和界面分子识别反应过程中配体或中间配合物的吸附都是在界面催化下进行的。这些发现是有用的溶剂萃取系统的设计考虑到界面的催化作用。结果表明，金属配合物在界面上的聚集比在体相中更容易。同时，界面聚集体对核酸碱基和二嗪异构体也表现出了新的分子识别能力。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.