DESIGN AND SYNTHESIS OF HIGHLY SELECTIVE ION ASSOCIATION REAGENTS BASED ON THE ANALYSIS OF AQUEOUS ION ASSOCIATION AND THEIR STUDY IN ANALYTICAL CHEMISTRY

分析了水溶液和水/有机混合溶液中的离子缔合平衡，并利用毛细管电泳精确测量离子迁移率的新方法获得了它们的离子缔合常数。结合离子缔合平衡的结果，提出了离子缔合试剂设计的指导原则、敏感离子缔合试剂的实用设计与合成以及基于离子缔合的新型分析方法，并对Motomizu提出的离子缔合概念进行了改进。(1)准确、精密的弱离子缔合平衡分析方法。用该方法分析了水溶液和水/有机溶剂混合溶液（乙醇、二氧六环和乙腈）中的弱离子缔合平衡。对所得结果进行了评价，并与Bjerrum方程和类似方程的预期结果进行了比较。研究了硝基苯酚、硝基苯甲酸盐和芳香磺酸盐在水相和胶束相之间的分布平衡；并与溶剂萃取的结果进行了比较和解释。(2)新型离子缔合试剂的开发。通过对离子周围微环境的控制，研制出高选择性、高灵敏度的离子缔合试剂。特别是设计合成了具有较大摩尔吸收率的平面型单价离子缔合试剂。这些试剂即使在碱性溶液中也非常稳定，并且将用于开发水相和水/有机相或水/胶束相分析物的敏感和选择性检测反应。(3) Stokes半径、疏水测度和群体贡献值的确定。这些数值/测量是在毛细管电泳对水溶液中离子迁移率的精确测量的基础上确定的。它们对于考虑离子的疏水性和设计新型离子结合试剂用于分析物离子的分离和检测具有重要意义。(4)离子物质分离测定新方法。在离子缔合的基础上，开发了新的分离/测定方法：例如，(a)用含有磺酸基的新试剂衍生化法测定伯胺，(b)用有机磺酸试剂衍生化后测定含氮药品，(c)饮用水中痕量溴酸盐，(d)氨基酸的分离和测定，以及(e)开发用于金属和非金属收集/浓缩试剂的新型试剂及其在痕量分析中的应用。少

Ion association equilibriums in aqueous and aqueous/organic mixed solutions were analyzed, and their ion association constants were obtained by using a newly developed analysis method based on the accurate ionic mobility measurement method with capillary electrophoresis. Considering the results obtained for the ion association equilibrium, a guid principle for designing ion association reagents, the practical design and synthesis of sensitive ion association reagents and novel analytical methods based on ion association were developed, and also the concept of ion association proposed by Motomizu was much improved.(1)Accurate and precise analysis method for weak ion association equilibrium. Weak ion association equilibriums in an aqueous solution and aqueous/organic solvent mixed solutions (ethanol, dioxane and acetonitrile) were analyzed by using the proposed analysis method. The results obtained were evaluated and compared with those expected from the Bjerrum and similar equation.The … More distribution equilibrium of nitrophenolates, nitrobenzoates and aromatic sulfonates between an aqueous and a micellar phase was examined; the results were compared and explained with those of solvent extraction.(2)Development of novel ion association reagents. Highly selective and sensitive ion association reagents were developed by controlling micro-environment around ions. Especially, planar monovalent ion association reagents, which possess large molar absorptivity, were designed and synthesized. Such reagents were very stable even in alkaline solutions, and will be useful for developing sensitive and selective detection reactions for analytes in aqueous and aqueous/organic or aqueous/ micellar phase.(3)Determination of Stokes' radii, hydrophobic measure and group contribution values. Such values/measures were determined on the basis of the accurate measurement of ionic mobility in an aqueous solution by capillary electrophoresis. They are very useful for considering the hydrophobicity of ions and designing novel ion association reagents for separation and detection of analyte ions.(4)Novel methods for separation and determination of ionic substances. On the basis of ion association, novel separation/determination methods were developed : for examples, (a) determination of primary amines based on derivatization with new reagents possessing a sulfonic group, (b) determination of nitrogen-containing pharmaceutical substances after derivatization with organic sulfonate reagents, (c) trace amounts of bromate in drinking waters, (d) separation and determination of amino acids, and (e) development of novel reagents for collection/concentration reagents for metals and non-metals and their application to trace analysis. Less