DESIGN AND SYNTHESIS OF HIGHLY FUNCTIONAL ION ASSOCIATION REAGENTS BASED ON THE CONTROL OF MICROENVIRONMENT AROUND IONS AND THEIR APPLICATION TO ANALYTICAL CHEMISTRY

设计并合成了几种高效离子缔合试剂，用于发展痕量分析的选择性分离和灵敏分析方法。使用合成的离子缔合试剂和研制的试剂，根据准确测量的离子缔合反应中阴离子的迁移率变化，用该方法测定了一些离子缔合常数。此外，还从离子迁移率的角度评价了离子的疏水性、亲水性和斯托克斯半径等特性。从本研究中获得的多种离子缔合物的离子缔合常数来看，Motomizu提出的离子缔合能力的概念是非常通用的，适用于真实的离子缔合试剂和/或反应。以下是本研究取得的主要成果。设计合成新型离子缔合试剂，通过改变烷基链长、有机基团种类等有机基团来控制离子周围的微环境。开发毛细管精确测定离子迁移率的测量方法。发展利用离子缔合过程中离子迁移率变化来分析水溶液中离子缔合平衡的方法。从离子活度的角度阐明水的结构与离子周围微环境的关系。开发几种高灵敏度测定痕量和超痕量分析物的方法，特别是在超纯水中：基于离子形成的几个ppt-subppb水平的磷酸盐和硅酸盐。采用毛细管电泳衍生化联用技术，建立烷基胺类似物和含氨基药物的分离及灵敏检测方法。

Several kinds of highly functional ion association reagents were designed and synthesized, and were used for developing selective separation and sensitive analysis methods for trace analytes. By using the synthesized ion association reagents and developed reagents, a number of ion association constants were determined using the method based on the accurately measured mobility, changes of anions through ion association reactions. Furthermore, the characteristics of ions, such as hydrophobicity, hydrophilicity and Stokes radii, are evaluated from the ionic mobilities. From the ion association constants obtained in this research for many kinds of ion associates, the concept, of ion associability proposed by Motomizu is very versatile and applicable to real ion association reagents and/or reactions. The following subjects are the main results obtained in this research.1. Design and synthesis of novel ion association reagents, whose micro-environment around ions are controlled by changing the organic groups, such as alkyl-chain length and kinds of organic groups.2. Development of the measurement method for the determination of accurate mobilities of ions using capillary.3. Development of the analysis methods for ion association equilibria in aqueous solutions using mobility changes of ions through ion association.4. Clarification of the relationship between water structure and micro-environment around ions on the basis of ionic mobilities.5. Development of several methods for highly sensitive determination of trace and ultratrace analytes, especially in ultrapurified waters : phosphate and silicate at several ppt -sub-ppb levels based on the formation of ion6. Development of the separation and the sensitive detection methods for alkyl-amine analogues and pharmaceuticals containing amino groups by using capillary electrophoresis coupled with the derivatization reaction.