DESIGN AND SYNTHESIS OF MULTI-FUNCTIONAL ION ASSOSIATION REAGENTS AND ITS APPLICATION TO SEPARATION AND ANALYSIS OF IONIC SUBSTANCES

多功能离子缔合试剂的设计合成及其在离子物质分离分析中的应用

• 批准号: 05453067
• 负责人: MOTOMIZU Shoji
• 金额: $ 4.42万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453067/
• 关键词: Sythesis of ion association reagents; anionic dyes; cationic dyes; ion association in aqueous medium; liquid-liquid distribution; ion association; coloration reactions; capillary electrophoresis; 試薬設計合成; イオン会合; 水溶液発色反応

Multi-functional ion Association reagents were designed and synthesized : they are 4 kinds of anionic dyes and three kinds of cationic reagents.We aimed at developing the reagents possessing the follwing functions : "(1)" function of determination - high sensitivity, "(2)" separation function - high extractability of ion associates, "(3)" ion associability - ion association in aqueous mediums, "(4)" function of hydrophobic interaction and "(5)" function of convenience - solubility, chemical stability, easy sythesis. 1. Anionic reagents. The newly synthesized anionic reagents were twenty derivatives of azo dyes containing sulfonic group, twenty-five derivatives of polynitrophenyl azo dyes containing hydroxyl group, six derivatives of triphenylmethane dyes and seven derivatives of polynitrodiphenyl-amines, and were examined with respect of the functional analytical regents.2. Cationic reagents. The newly synthesized cationic reagents were twenty-five derivatives of alkylpyridiniums, ten derivatives of azo dyes, five derivatives of triphenylmethane dyes, and were examined by using spectrophotometry, stopped-flow method and high-stirring interface-adsorption method. 3. Ideal regents. Azo dyes possessing long-chain alkylamino groups and a sulfonic group satisfied all the five funtions, and polynitrophenylazo dyes possessing hydroxyl group showed the solvatochromism toward longer wavelengths when they formed ion associates in aueous mediums. Triphenymethane dyes possessing bulky groups near the centered carbon were stable even in alkaline mediums and promising as a ion association reagent. Of the cationic reagents, dichloro derivatives of Malachite Green was a useful reagent as a cationic pairing ion. These reagents were applied to the development of new methods for separation and determination of ionic substances.

设计合成了4种阴离子染料和3种阳离子缔合试剂，旨在开发具有以下功能的试剂：(1)“测定功能--高灵敏度”；(2)“分离功能--离子缔合物的高萃取率”；(3)“离子缔合能力--水介质中的离子缔合能力”；(4)“疏水作用功能”；“(5)”方便--溶解、化学稳定、易于合成“功能。1.阴离子试剂。新合成的阴离子试剂包括20个含磺酸基的偶氮染料衍生物、25个含羟基的聚硝基苯基偶氮染料的衍生物、6个三苯基甲烷染料的衍生物和7个多硝基二苯胺的衍生物，并对其功能分析试剂进行了考察。阳离子试剂。新合成的阳离子试剂包括25个烷基吡啶衍生物、10个偶氮染料衍生物、5个三苯基甲烷染料衍生物，并用分光光度法、停流法和高搅拌界面吸附法进行了表征。3.理想的摄政者。含长链烷氨基和磺酸基的偶氮染料满足上述五种功能，含羟基的聚硝基苯偶氮染料在水介质中形成离子缔合物时，表现出向长波方向的溶致变色。三苯甲烷染料在中心碳附近具有较大的基团，即使在碱性介质中也很稳定，有望作为离子缔合试剂。在阳离子试剂中，孔雀石绿的二氯衍生物是一种有用的阳离子配对试剂。这些试剂被应用于开发分离和测定离子物质的新方法。

项目成果

S.Motomizu: "Ultra trace determination of phosphate ion based on filtration-dissolution and flow-through spectrophotometric measurement" Analytical Sciences. 11. 155-160 (1995)

S.Motomizu：“基于过滤溶解和流通分光光度测量的磷酸根离子的超痕量测定”分析科学。

Shoji Motomizu: "Flow injection method coupled with solvent extraction using on-tube visible absorption and application to the determination of anionic surfactants" Journal of Flow Injection Analysis. 10. 255-261 (1993)

Shoji Motomizu：“流动注射方法与使用管上可见光吸收的溶剂萃取相结合，及其在阴离子表面活性剂测定中的应用”《流动注射分析杂志》。

N.Goto, M.Oshima and S.Motomizu: "Determination of phosphate and arsenate by a flotation-pairing ion exchange/extraction method." Bunseki Kagaku. 42. 151-157 (1993)

N.Goto、M.Oshima 和 S.Motomizu：“通过浮选配对离子交换/萃取法测定磷酸盐和砷酸盐。”

S.Motomizu, T.Hagiwara, A.Yokoyama and M.Oshima: "Color development based on the ion association of molybdophosphate with cationic dye Chloro-Malachite Green" Anal.Sci.9. 817-820 (1993)

S.Motomizu、T.Hagiwara、A.Yokoyama 和 M.Oshima：“基于钼磷酸盐与阳离子染料氯孔雀石绿离子缔合的颜色开发”Anal.Sci.9。

S.Motomizu: "Separation and sensitive determination of metal ions by capillary zone electrophoresis with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)-phenol" Analyst(London). 119. 1787-1792 (1994)

S.Motomizu：“使用 2-(5-溴-2-吡啶基)-5-(N-丙基-N-磺基丙氨基)-苯酚通过毛细管区带电泳分离和灵敏测定金属离子”分析师（伦敦）。