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

本研究的目的是发明一种新的液-液界面上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的动力学反应机理。得到了以下有用的结果：1)用单分子探针法评价界面的纳米性质利用荧光显微镜追踪界面上吸附的单个荧光分子。根据观测结果，首次计算了界面处的扩散系数和界面黏度。评价了共吸附表面活性剂分子对单分子扩散的影响。2)界面反应直接测量方法的发明离心液膜法在各种溶剂萃取体系中的实用性得到了证实。为了测量快至几微秒的快速界面反应，构建了一种新型的微鞘流荧光显微镜。此外，还发明了离心液膜/拉曼显微镜和微-两相质谱法。3)界面催化和界面上的分子识别在反应过程中，当发生配体或中间配合物的吸附时，总是催化界面上的络合。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。结果表明，金属配合物在界面处比在体相处更容易聚集。同时，界面聚集对核酸碱基和嘧啶异构体表现出新的分子识别能力。4)界面的分子模拟成功地将分子模拟方法应用于配体界面吸附能的估计。

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.