Improvement of sensitivity for chemiluminescnt detection system using complex

研究了三（2,2′-联吡啶）钌（III）与多种化合物的化学发光反应。五元杂芳香化合物产生强烈的辐射。化学发光强度随芳香环电子密度的增加而增加。在α-位置有一个羧基的脂肪族仲胺表现出很强的化学发光。详细研究了三（2,2′-联吡啶）钌（III）与2,5-二甲基噻吩的化学发光反应。三（2,21-联吡啶）钌（III）与2,5-二甲基噻吩以2:1的比例反应。反应产物经鉴定为5-甲基-2-噻吩乙醛。通过对噻吩衍生物的化学发光强度和氧化电位的同时测定，结合已有的对其氧化反应的研究，估计了涉及去质子化的化学发光反应机理。鉴于人体体液中的亚胺酸是多种疾病的重要生物标志物，本文建立了一种灵敏的同时测定人血清中亚胺酸的方法。四种亚胺酸在60分钟内成功测定。为了开发新型电化学发光（ECL）免疫检测的共反应物，对三（2,2’-联吡啶）钌（II） ECL检测系统进行了初步研究。结果表明，三（2,2′-联吡啶）钌(II)/ N，N-二丙基- l-丙氨酸体系的灵敏度与三（2,2′-联吡啶）钌(II)/三丙胺体系相当，该体系已被广泛应用。由于N，N-二丙基- l-丙氨酸在常温下为固体，水溶液为中性，与三丙胺相比，使用方便。合成了一种用于电合成三（2,4,5-三甲基-3-噻吩）钌（III）化学发光检测的新型衍生试剂（2,4,5-三甲基-3-噻吩）乙酸。采用高效液相色谱法可对混合溶液中的13种烷基酚和双酚A进行ppb级的检测。建立了环境水中磷酸盐的灵敏测定方法。磷酸与钼酸盐在硫酸中反应生成的磷酸钼与脂肪族叔胺形成离子对。采用三（2,2′-联吡啶）钌（III）化学发光法间接测定离子对中脂肪族叔胺的含量。少

The chemiluminescent reaction of tris(2,2'-bipyridine)ruthenium(III) with various compounds was examined. Five-membered heteroaromatic compounds produced intense emission. The chemiluminescent intensity increased with an increase in electron density of the aromatic ring. Aliphatic secondary amines having a carboxyl group at the α-position showed very intense chemiluminescence. The chemiluminescent reaction of tris(2,2'-bipyridine)ruthenium(III) with 2,5-dimethylthiophene was examined in detail. Tris(2,21-bipyridine)ruthenium(III) reacted with 2,5-dimethylthiophene in the ratio of 2:1. The reaction product was identified as 5-methyl-2-thiophenecarbaldeyde. From the simultaneous measurement of the chemiluminescent intensity and the oxidation potential and previously reported studies on the oxidative reaction of thiophene derivatives, the chemiluminescent reaction mechanism involving deprotonation was estimated. Since imino acids in human body fluid are important biomakers for various ill … More nesses, a sensitive simultaneous determination method for imino acids in human serum was developed. Four imino acids were successfully determined within 60 min.To develop novel co-reactants for electrochemiluminesecence (ECL) immunoassays, preliminary studies on the tris(2,2'-bipyridine)ruthenium(II) ECL detection system using some compounds as co-reactants were performed. It was suggested that the sensitivity of the tris(2,2'-bipyridine)ruthenium(II)/ N,N-dipropyl-L-alanine system was comparable to that of the tris(2,2'-bipyridine)ruthenium(II)/ tripropylamine system, which has been widely used. Since N,N-dipropyl-L-alanine is a solid at ordinary temperature and its aqueous solution is neutral, it is ease of use compared to tripropylamine. A novel derivatization reagent, (2,4,5-trimethyl-3-thieny)acetic acid, for electrogenerated tris(2,2'-bipyridine)ruthenium (III) chemiluminescent detection was synthesized. Thirteen alkylphenols and bisphenol A in a mixed solution could be detected at ppb levels using high performance liquid chromatography. A sensitive determination method of phosphate in environmental water was developed. Molybdophosphate produced by the reaction of phosphate with molybdate in sulfuric acid formed an ion-pair with aliphatic tertiary amines. Phosphate was indirectly determined by the measurement of the aliphatic tertiary amines in the ion-pairs with tris(2,2'-bipyridine)ruthenium(III) chemiluminescent detection. Less