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

具有吸光特性的离子缔合试剂的合成及其在水溶液中离子缔合中的应用

• 批准号: 09440251
• 负责人: MOTOMIZU Shoji
• 金额: $ 8.77万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-09440251/
• 关键词: ion association reagents; solvatochromism; visible absorption; capillary electrophoresis; equilibrium analysis; aqueous media; ionic hydrophobicity; analysis of hydrophobic ion; N-アルキルフェニルアゾアニリン; ニトロフェニルアゾフェノール; アゾ系陽イオン試薬; キャピラリー電気泳動法; イオン会合平衡

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.

合成了新型离子缔合试剂，并研究了其作为分析试剂用于吸光光度法和荧光光度法测定水溶液中的阳离子和阴离子。这里合成的试剂具有改变其可见光吸收特性的能力，当它们与配对的分析物离子反应形成离子缔合物时。可见光吸收的变化是由于离子缔合物的最大吸收峰发生蓝移或红移，这被认为是一种“溶致变色现象”。当试剂与其配对离子反应以形成离子缔合物并将试剂的微环境从亲水场改变为疏水场时，可以发生离子缔合试剂的这种溶剂化变色。本文合成了一类新的溶剂化显色离子缔合试剂，它们是苯偶氮阴离子、三苯甲烷阳离子、二苯胺阴离子和苯偶氮苯胺阳离子的类似物。用分光光度法考察了试剂的离子缔合能力，并根据实验结果总结了影响离子缔合能力的因素。所开发的试剂应用于水溶液中疏水配对离子的分光光度测定，并且还应用于离子表面活性剂作为终点指示剂的滴定方法。采用精确的迁移率测量方法，建立了水溶液中离子缔合反应的分析方法，并应用于水溶液中离子缔合平衡的分析。在此基础上，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，在水介质中的离子缔合反应的重要性，作为一个基本的反应和有用的分析试剂用于测定疏水阴离子。

项目成果

S.Motomizu: "Ion association and its reaction mechanism (Review)"BUNSEKI KAGAKU. 48. 151-181 (1999)

S.Motomizu：“离子缔合及其反应机理（综述）”文石化学。

L.C.Manege et al.: "Analysis of ion association reactions in aqueous solutions between alkali metal-crown ether complexes and pairing anions by capillary zone electrophoresis"Analyst. 125. 699-703 (2000)

L.C.Manege 等人：“通过毛细管区带电泳分析水溶液中碱金属冠醚配合物与配对阴离子之间的离子缔合反应”分析员。

L.C.Manege: "Ion association reactions in aqueous solutions between non-UV-absorbing crown ether-alkali metal complexes with picrate ion by CZE"The Analyst. 125. 1928-1932 (2000)

L.C.Manege：“CZE 分析非紫外线吸收性冠醚-碱金属配合物与苦味酸根离子在水溶液中的离子缔合反应”The Analyst。

T.Takayanagi et al.: "Electrophoretic mobility study of ion association between aromatic anions and quaternary ammonium ions…"Analyst. 122. 57-62 (1997)

T. Takayanagi 等人：“芳香族阴离子和季铵离子之间离子缔合的电泳迁移率研究……”分析师 122. 57-62 (1997)

L.C.Manege et al.: "Ion association reactions in aqueous solutions between non-UV-absorbing crown ether-alkali metal complexes …"Analyst. 125. 1298-1932 (2000)

L.C.Manege 等人：“非紫外线吸收冠醚-碱金属络合物之间水溶液中的离子缔合反应……”分析师 125. 1298-1932 (2000)