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

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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.