Measurements of Non-Equilibrium State for Reactions at Liquid-Liquid Interfaces and the Analysis of Selective Distribution Behaviors

作为液液界面反应的测量方法，共振二次谐波(RSH)光谱和时间分辨全内反射荧光光谱(TIRF)被发展并应用于表征在液-液界面吸附的分子。此外，还建立了电解液滴加电极的电位扫描极谱，用于液-液界面络合动力学的分析。在RSH光谱方面，罗丹明B(Rh-B)作为吸附在液-液界面的分子进行了研究。与主体溶液相比，RH-B分子稳定在庚烷-水界面。基于RSH光谱的浓度依赖关系，发现在高体浓度时，界面上的分子可以以单体和二聚体的混合物形式存在。估算了Rh-B的分子取向，在低浓度时取向角几乎恒定为65度，…角减小用时间分辨的TIRF研究了8-苯胺基-1-萘磺酸盐分子在庚烷-水界面的微环境。通过分析荧光衰变曲线，发现界面附近的荧光团以两种不同的溶剂化结构存在。其中一个位于离界面几纳米的地方，另一个位于水相相对较宽的范围内。前者的溶剂化结构是荧光寿命较长的原因，反映了微环境的低极性或极高粘度。对于液-液界面上的化学反应，通过测量动态界面张力和界面上的离子转移，研究了8-喹啉衍生物与二价金属离子的络合动力学。结果表明，5-辛氧甲基-8-喹啉具有界面吸光效应，其吸光系数与反阴离子和有机相有关。这些依赖关系可用离子对形成常数和络合剂的分配系数来解释。通过对界面离子迁移的测量表明，络合作用发生在靠近有机相的界面上。如上所述，建立了几种分析液-液界面反应的方法，发现界面上的反应与钝化溶液中的反应不同。较少

As measurement methods for reactions at liquid-liquid interfaces, the resonat second harmonic (RSH) spectroscopy and the time resolved total internal reflection fluorescence spectroscopy (TIRF) were developped and applied to characterize molecules absorbed at liquid-liquid interfaces. In addition, the potential-scan polarography with an electrolyte dropping electrode was developped for the analysis of the complexation kinetics at liquid-liquid interfaces.As for RSH spectroscopy, rhodamine B (Rh-B) is studied as a moleule adsorbed at liquid-liquid interfaces. Rh-B molecules were found to be stabilized at the heptane-water interface compared bulk solutions. Based on the concentration dependence of RSH spectra, it was found that molecules at the interface can exist as a mixture of monomer and dimer when the bulk concentration is high. Molecular orientations of Rh-B were estimated and the orientation angle was almost constant as 65 degree when the concentration is low, and the angle decrea … More sed at higher concentrations.A time resolved TIRF was applied to study the microenvironments of 8-anilino-1-naphthalenesulfonate molecules at the heptane-water interface. By analysing the fluorescence decay profiles, it was found that the fluorophores in the vicinity of the interface are present in two different solvated structures. One of them is located up to a few nanometers from the interface, and the other is located in a relatively wide range twoard the aqueous phase. The former solvated structure is the cause of a long fluorescence lifetime which reflects the low polarity or the extremely high viscosity of the microenvironments.As for chemical reactions at liquid-liquid interfaces, complexation kinetics were examined using 8-quinolinol derivatives and divalent metal ions by measuring dynamic interfacial tension and ion transfer across the interface. As a result, it was found that 5-octyloxymethyl-8-quinolinol showed interface absorptivity and the adorptivity depended on both the counter anion and the organic phase. These dependence was explained by the ion pair formation constant and the distribution coefficient of a chelating reagent. From the measurement of an ion tranfer across the interface, it was suggested that the complexations occured at the interface nearer to the organic phase.As mentioned above, several methods were establishied to analyze reactions at liquid-liquid interfaces, and the reactions at the interface were found to be different from those in bluk solutions. Less