Design of new ion association reagents having light absorption and thermo-dependence and analysis of ion association mechanism

具有光吸收和热依赖性的新型离子缔合试剂的设计及离子缔合机理分析

• 批准号: 13640609
• 负责人: SAKAI Tadao
• 金额: $ 2.3万
• 依托单位: Aichi Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640609/
• 关键词: ternary ion associates; synergistic extraction effect; fluorescence derivatives; formaldehyde; catalytic reaction; flow injection analysis; ion association titration; tetrabromophenolphthalein ethyl ester; 第4級アンモニウム塩の微量分析; イオン会合反応; 目視検出法(可視吸収) /

1) Xanthene dyes such as eosin and tetraiodofluorescein form 1 : 2 ion associates with quaternary ammonium ions at pH 7-9 ; however, the development of color in the organic solvent is poor. When a quaternary ammonium salt is added in the etractable 1 : 2 associate formed between a xanthene dye and a cinchona-alkaloid in the neutral media, a mixed ternary ion associate (1 : 1 : 1) is formed. Its extractability is enhanced due to the more bulky association formation. The ion association caused by addition of cinchona-alkaloids is unique. Eosin and tetraiodofluorescein are useful for the determination of trace amounts of quaternary ammonium salts.2) The slow redox reaction of cysteine with iron(III) in the presence of 1,10-phen is catalyzed by copper(II), producing an iron(II)-phen complex> The color development is applied to the determination of cysteine spectrophotometrically. The limit of detection(3σ) is 5 x 10^<-7> M and RSD is 0.4%. Many other amino acids do not interfere, however, … More reducing and oxidizing substances gave strong interferences. And also, a spectrophotometric method was developed for the simultaneous analysis of ascorbic acid and cysteine by flow injection system equipped with a double flow cell, which was installed in a double-beam spectrophotometer. Copper(II) greatly accelerated the reduction reaction of iron(III) with cysteine, while with ascorbic acid was little affected by copper(II). On the basis of the difference in the rate between the two reactions, both substances can be determined.3) Stepwise titrimetric method is developed for the simultaneous determination of pharmaceutical quaternary ammonium salts and aromatic amines. The method is based on the solvent extraction of R_4N and R_3NH with an ion association reagent, tetrabromophenolphthalein ethyl ester (TBPE). When the samples containing these compounds are titrated with tetrakis(4-fluorophenyl) borate or tetraphenylborate, the color in organic phase turned to blue, red-violet and yellow and the first end point and second end point were determined, respectively. Less

1)曙红、四碘荧光素等黄色染料在pH 7~9范围内与季铵离子形成1：2的缔合离子，但在有机溶剂中显色较差。当在中性介质中将季铵盐加入到黄原染料与金鸡纳生物碱形成的1：2缔合物中时，形成混合三元离子缔合物(1：1：1)。由于形成了更大的缔合，其可萃取性得到了增强。金鸡纳生物碱的加入引起的离子缔合是独一无二的。曙红和四碘荧光素可用于痕量季铵盐的测定。2)在1，10-phen存在下，半胱氨酸与Fe(III)的缓慢氧化还原反应被铜(II)催化，生成Fe(II)-phen络合物&GT；显色用于半胱氨酸的光度测定。方法检出限(3σ)为5×10~(-7)M，相对标准偏差为0.4%。然而，许多其他氨基酸不会干扰…还原和氧化物质越多，干扰越强。同时，建立了双流池流动注射系统同时测定抗坏血酸和半胱氨酸的光度分析方法。铜(II)极大地促进了铁(III)与半胱氨酸的还原反应，而对抗坏血酸的还原反应几乎不受铜(II)的影响。3)建立了同时测定药物季铵盐和芳香胺的分步滴定方法。该方法基于离子缔合试剂四溴苯酚邻苯二甲酸乙酯(TBPE)对R4N和R3NH的萃取。用四(4-氟苯基)硼酸盐或四苯基硼酸酯滴定含有这些化合物的样品时，有机相的颜色分别变为蓝色、红紫色和黄色，并分别测定了第一终点和第二终点。较少

项目成果

T.Sakai, S.Tanaka, N.Teshima, S.Yasuda, N.Ura: "Fluorimetric flow injection analysis of trace amount of formaldehyde in environmental atmosphere with 5,5-dimethvlcyclohexane-1,3-dione"Talanta. 58. 1271-1278 (2002)

T.Sakai、S.Tanaka、N.Teshima、S.Yasuda、N.Ura：“使用 5,5-二甲基环己烷-1,3-二酮对环境大气中痕量甲醛进行荧光流动注射分析”Talanta。

Tadao Sakai: "Fluorimetric flow injection analysis of trace amount of formaldehyde in environmental atmosphere with 5,5-dimetylcyclohehane-1,3-dione"Talanta. 59. 1271-1278 (2002)

Tadao Sakai：“使用 5,5-二甲基环己烷-1,3-二酮对环境大气中痕量甲醛进行荧光流动注射分析”Talanta。

Tadao Sakai: "Stepwise Determination of Quaternary Ammonium Salts and Aromatic Amines in Pharmaceuticals by Ion Association Titration"Analytical Sciences. 17. 1379-1382 (2001)

Tadao Sakai：“离子缔合滴定法逐步测定药物中的季铵盐和芳香胺”分析科学。

酒井忠雄: "シーケンシャルインジェクションアナリシス"ぶんせき. No.6. 289-295 (2001)

Tadao Sakai：“顺序注射分析”Bunseki No.6 (2001)。

手嶋 紀雄: "システインの吸光光度定量への銅(II)接触作用の利用"分析化学. 50. 47-51 (2001)

Norio Teshima：“利用铜 (II) 接触作用进行半胱氨酸的分光光度测定”《分析化学》50. 47-51 (2001)。