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

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。

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.