SYNTHESIS OF ION ASSOCIATION REAGENTS POSSESSING CHARACTERISTIC LIGHT ABSORBING AND ITS USE IN ION ASSOCIATION IN AQUEOUS SOLUTION

合成了一种新型离子缔合试剂，并将其作为吸光度和荧光法测定水溶液中阳离子和阴离子的分析试剂。当它们与成对的分析物离子反应形成离子缔合物时，这里合成的试剂具有改变其可见光吸收特性的能力。可见光吸收的变化是由于离子缔合试剂的吸收峰蓝移或红移所致，被认为是一种“溶致变色现象”。离子缔合试剂与其配对离子反应形成离子缔合物，使试剂的微环境由亲水场变为疏水场时，就会发生这种溶致变色性。新合成了多种溶致变色离子缔合试剂，它们是苯偶氮阴离子、三苯甲烷阳离子、二苯胺酸盐离子和苯基偶氮苯胺离子的类似物。用分光光度法检测了这些试剂的离子缔合能力，总结了影响离子缔合能力的因素。将所研制的试剂用于水溶液中疏水配对离子的光度测定，并作为终点指示剂应用于离子表面活性剂的滴定方法。利用精确迁移率测量法建立了分析水溶液中离子缔合反应的方法，并将其应用于水溶液中离子缔合平衡的分析。根据得到的平衡常数，总结了试剂的离子缔合性、影响离子缔合性的因素以及离子的疏水性。这些数据表明了离子缔合反应在水介质中作为基本反应之一的重要性，以及作为测定疏水阴离子的分析试剂的有效性。

Novel ion association reagents were synthesized and investigated as analytical reagents for absorptiometric and fluorimetric determination of cationic and anionic ions in aqueous solutions. The reagents synthesized here possess the ability to change their visible light-absorbing characteristics when they react with pairing analyte ions to form ion associates. The change in the visible light absorption is due to the blue or red shift of the absorption maxima of the ion association reagents, which is considered to be a kind of "solvatochromism phenomenon". Such solvatocromism of the ion association reagents can occur when the reagents react with their pairing ions to form ion associates and change the micro-environment of the reagents from hydrophilic to hydrophobic field. Various kinds of solvatochromic ion association reagents were newly synthesized ; they are the analogues of phenylazo anions, triphenylmethane cations, diphenylaminate ions and phenylazoanilinium ions. Ion associability of these reagents were examined by spectrophotometry ; from the results obtained the factors affecting the ion associability were summarized. The reagents developed were applied to the spectrophotometric determination of hydrophobic pairing ions in aqueous solutions, and were also applied to the titrimetric method of ionic surfactants as an end-point indicator. The method for the analysis of ion association reactions in aqueous solutions was developed by using the accurate mobility measurement method, and was applied to the analysis of ion association equilibria in aqueous solutions. On the basis of the equilibrium constants obtained, the ion associability of the reagents and the factors affecting the ion associability, as well as the hydrophobicity of ions, were summarized. Such data demonstrate the importance of the ion association reaction in aqueous media as one of the fundamental reactions and the usefulness as an analytical reagent for the determination of hydrophobic anions.