New Approaches to Chemical System Designing in Kinetic-Differentiation Capillary Electrophoresis Separations of Metal and Molecular Complexes.

本研究项目的目的是通过更好地理解CE分离的基本溶液化学，以及分成有机合成方法学和计算化学的衍生配体的分子设计方法，开发用于金属和分子络合物的新型CE分离模式。(1)离子迁移率受电致导电性缓冲溶液中的离子-离子相互作用控制；(2)研究了2，2‘-二羟基偶氮苯-5，5’-二磺酸盐与Al(III)、Ga(III)和In(III)的络合物在毛细管中的解离动力学，提出了一种通过用酸性缓冲溶液对毛细管进行预处理来控制电渗流动的新方法。(3)将凝胶应用于…。更多的是使用聚丙烯酰胺和纤维素作为凝胶基质来监测自然产生的腐殖酸和黄腐酸有机物。开发了多种硫杂杯芳烃类化合物的制备新方法，并从金属离子识别和手性分离两个方面考察了它们在CE分离体系中的适用性。尝试了一种基于计算化学的分子设计方法，结合密度泛函计算、量子分子动力学、蒙特卡罗方法和计算机图形学构建了一个完整的计算系统。该系统使人们能够在有限的温度和压力下快速计算配体的电子态和结构，这有望成为在预测命题的基础上进行分子设计的一个非常有用和通用的工具。较少

The aim of this research project is the exploitation of novel CE separation modes for metal- and molecular complexes via a better understanding of the underlying solution chemistry of the CE separation, and the molecular designing approach for derivatizing ligands bifurcaied into the organic synthesis methodology and the computational chemistry.(1) Ionic mobilities are controlled by ion-ion interactions in eiectropnoretic buffer solutions ; an addition of polymer electrolyte such as poly(diallyldimethyi ammonium chioride) was found to be very effective for the fine separation of anionic metal chelates of poiyaminocarboxyiaies, EDTA, Quin 2, and HBED complexes.(2) The dissociation kinetics of 2,2'-dihydroxyazobenzene-5,5'-disulfonate chelates of AI(III), Ga(III), and In(III) ions in a CZE system were investigated, developing a new method for electroosmotic flow control by the pretreatment of the capillary tube with an acidic buffer solution.(3) Gel (molecular Sieving) CE was applied to … More the monitoring of naturally-occurring organics of humic and fulvic acids using polyacrylamide and cellulose as gel matrices. This methodology makes good contribution to the water quality assessment technology.(4) Some new methods were developed for the preparation of various kinds of thiacalixarenes compounds, and the suitability for the CE separation systems was examined in terms of metal ion recognition and chiral separations. Also it was found that a certain kind of this ligand specifically works as a receptor for haloorganics.(5) An approach of the molecular designing based on the computational chemistry was attempted ; an integrated computational system was constructed with the aid of density functional calculations, quantum molecular dynamics, the Monte Carlo method, and computer graphics. This system enables ones to make a fast calculation of the electronic states and structures of ligands under finite temperature and pressure, which is expected to be a very helpful and versatile tool for the molecular designing on a predicted proposition basis. Less