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

基于离子微环境控制的高功能离子缔合试剂的设计与合成及其在分析化学中的应用

• 批准号: 13440220
• 负责人: MOTOMIZU Shoji
• 金额: $ 9.66万
• 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: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440220/
• 关键词: ION ASSOCIATION; SOLVATOCHROMISM; CATIONIC AZO DYES; CATIONIC CYANINE DYES; MICROENVIRONMENT OF IONS; IONIC MOBILITY; ION ASSOCIATION CONSTANTS; ION ASSOCIABILITY CONCEPT; アゾ系陰イオン試薬; ストークス半径; ミクロ環境制御; イオン会合試薬; 疎水性尺度; 置換基寄付; 移動度測定法; 水溶液反応

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.

设计并合成了几种高功能的离子缔合试剂，用于痕量分析物的选择性分离和灵敏分析。利用合成的离子缔合试剂和研制的离子缔合试剂，通过准确测量离子缔合反应中阴离子的迁移率、变化，用该方法测定了一系列离子缔合常数。此外，离子的特性，如疏水性，亲水性和斯托克斯半径，评价从离子迁移率。从本研究中得到的多种离子缔合物的离子缔合常数来看，Motomizu提出的离子缔合性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。本研究取得的主要成果如下：1.设计合成了新型离子缔合试剂，通过改变有机基团的链长和种类来控制离子周围的微环境.发展了利用毛细管技术精确测定离子迁移率的测量方法.利用离子缔合过程中离子迁移率的变化，发展水溶液中离子缔合平衡的分析方法.根据离子迁移率阐明了水的结构与离子周围微环境的关系.开发了几种高灵敏度测定痕量和超痕量分析物的方法，特别是在超纯净沃茨中：基于离子6的形成，在几个ppt -亚ppb水平上测定磷酸盐和硅酸盐。毛细管电泳衍生化反应联用分离及灵敏检测烷基胺类似物及含氨基药物的方法。

项目成果

本水昌二: "イオン会合と分析化学"ぶんせき. 2003. 734-736 (2003)

Shoji Motomizu：“离子关联和分析化学”Bunseki 2003. 734-736 (2003)。

T.Takayanagi, T.Ninomiya, S.Motomizu: "Separation of aromatic substances by micellar electrokinetic chromatography using surfactants possessing polyoxyethylene moiety."Anal.Sci.. 17,Suppl. a133-a136 (2001)

T.Takayanagi、T.Ninomiya、S.Motomizu：“使用具有聚氧乙烯部分的表面活性剂通过胶束电动色谱分离芳香族物质。”Anal.Sci.. 17，增刊。

J.Mbuna, T.Takayanagi, M.Oshima, S.Motomizu: "Investigation of weak ion association equilibria between inorganic anions and tetraalkylammonium ions in ethanol-aqueous media by capillary zone electrophoresis."Bull.Chem.Soc.Jpn.. (in press). (2004)

J.Mbuna、T.Takayanagi、M.Oshima、S.Motomizu：“通过毛细管区带电泳研究乙醇-水介质中无机阴离子和四烷基铵离子之间的弱离子缔合平衡。”Bull.Chem.Soc.Jpn..（

T.Tsuboi, Y.Hirano, Y.Shibata, S.Motomizu: "Sensitivity improvement of ammonia determination based on flow-injection indophenol spectrophotometry with manganese (II) ion as a catalyst and analysis of exhaust gas of thermal power plant"Analytical Sciences.

T.Tsuboi、Y.Hirano、Y.Shibata、S.Motomizu：“以锰 (II) 离子为催化剂的流动注射靛酚分光光度法提高氨测定的灵敏度以及火电厂废气分析”Analytical Sciences

J.Mbuna, T.Takayanagi, M.Oshima, S.Motomizu: "Evaluation of Weak Ion Association between Tetraalkylammonium Ions and Inorganic anions in Aqueous Solutions by Capillary Zone Electrophoresis."J.Chromatogr.A.. 1022. 191-200 (2004)

J.Mbuna、T.Takayanagi、M.Oshima、S.Motomizu：“通过毛细管区带电泳评估水溶液中四烷基铵离子和无机阴离子之间的弱离子缔合。”J.Chromatogr.A.. 1022. 191-200（