A Study on Dynamical Aspects of Analytical Reactions

本文将激光捕获-光谱-电化学技术与皮秒微光谱学相结合，研究了分析科学和分离科学中几种基本关键反应的动力学行为。离子交换动力学：在过去的几十年里，聚合物树脂珠中的离子交换反应得到了广泛的研究。尽管如此，基于单个聚合物珠测量的离子交换过程的直接观察从未被探索过。上述新技术已成功地应用于单个微米级聚合物微球的离子交换动力学研究。在直接测定离子交换过程与聚合物交联密度、离子交换基的反离子性质、温度等因素的关系的基础上，详细阐述了离子交换反应的影响因素。基于全内反射荧光光谱和动态荧光各向异性，研究了液/液界面发生的更多tic行为。在水/四氯化碳界面和水/二氯乙烷界面的情况下，已经证明水/四氯化碳界面的界面层比水/二氯乙烷界面的界面层更薄。采用类似的实验方法来阐明水/邻苯二甲酸酯界面的特性。从油本身的分子结构角度对结果进行了讨论。微滴/溶液界面化学的动力学方面：激光捕获微化学技术证明了微米级液滴尺寸对油滴/水界面的电子传递和传质速率的影响。液滴大小效应也证实了单个液滴中染料分子的分子关联以及单个微液滴中染料的荧光寿命。少

A laser trapping-spectroscopy-electrochemistry technique, developed by the present researchers, was combined the with picosecond microspectroscopy to study dynamical behaviors of several fundamental key reactions employed in analytical science and separation science.1. Ion-Exchange Dynamics : Ion-exchange reactions in polymeric resin beads have been extensively studied among past decades. Nonetheless, direct observation of the ion-exchange processes based on single polymer beads measurements has never been explored. The new echnique mentioned above was applied successfully to elucidate ion-exchange dynamics in single micrometer-sized polymer beads. On the basis of direct measurements of the ion-exchange processes as a function of the cross-linking density of the polymer, the nature of the counter ion of the ion-exchangeable group, temperature, and so forth, the factors determining the ion-exchange reactions were elucidated in detail.2. Dynamics at Liquid/Liquid Interfaces : Characteris … More tic behaviors occurring at liquid/liquid interfaces were studied on the basis of total-internal reflection fluorescence spectroscopy as well as by dynamic fluorescence anisotropy. In the case of water/carbon tetrachloride and water/dichloroethane interfaces, it has been demonstrated that the interfacial layer is thinner for the water/carbon tetrachloride interface as compared with that at the water/dichloroethane interface. Analogous experimental approaches were applied to elucidate characteristics at water/phthalate ester intefaces. The results were discussed in terms of the molecular structures of the oil itself.3. Dynamical Aspect of the Chemistry at Microdroplet/Solution Interfaces : The laser trapping-microchemistry technique demonstrated micrometer droplet size effects on electron transfer and mass transfer rates at oil droplet/water interfaces. Droplet size effects were also confirmed for molecular association of dye molecules in single droplets as well as for fluorescence lifetime of a dye in individual microdroplets. Less