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关于过氧草酸酯化学发光的机制。淬灭化学发光作为高效液相色谱中的一种检测方法。

On the mechanism of peroxyoxalate chemiluminescence. Quenched chemiluminescence as a detection method in HPLC.

作者信息

Gooijer C, van Zoonen P, Velthorst N H, Frei R W

机构信息

Free University, Department of General and Analytical Chemistry, Amsterdam, The Netherlands.

出版信息

J Biolumin Chemilumin. 1989 Jul;4(1):479-83. doi: 10.1002/bio.1170040163.

Abstract

Several analytes such as the inorganic anions bromide, iodide, sulphite and nitrite and organic compounds as substituted anilines and sulphur compounds cause quenching of peroxyoxalate chemiluminescence. A detection method for liquid chromatography based on the quenching phenomenon has been developed. It makes use of an immobilized luminophore, i.e. 3-aminofluoranthene covalently bound via an alkyl-spacer on controlled pore glass, packed in the detector cell. The mechanism behind the quenching has been elucidated by investigating the roles of luminophores (both in the liquid and in solid state) and oxalates in peroxylate CL with respect to quenchers. Most probably the quencher destroys the radical ion pair produced after electron transfer in the last stage of the CIEEL reaction scheme, thus preventing the formation of electronically excited luminophore.

摘要

几种分析物,如无机阴离子溴化物、碘化物、亚硫酸盐和亚硝酸盐,以及有机化合物如取代苯胺和硫化合物,会导致过氧草酸酯化学发光的猝灭。基于这种猝灭现象开发了一种液相色谱检测方法。它使用了一种固定化的发光体,即通过烷基间隔基共价结合在可控孔径玻璃上的3-氨基荧蒽,填充在检测池中。通过研究发光体(液态和固态)和草酸盐在过氧草酸酯化学发光中相对于猝灭剂的作用,阐明了猝灭背后的机制。最有可能的是,猝灭剂破坏了在CIEEL反应方案最后阶段电子转移后产生的自由基离子对,从而阻止了电子激发发光体的形成。

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