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Use of coumarin derivatives as activators in the peroxyoxalate system in organic and aqueous media
Journal of Photochemistry and Photobiology A: Chemistry ( IF 4.1 ) Pub Date : 2020-12-11 , DOI: 10.1016/j.jphotochem.2020.113076
Maidileyvis C. Cabello , Liena V. Bello , Wilhelm J. Baader

The peroxyoxalate system – base catalyzed reaction of oxalic ester derivatives with hydrogen peroxide in the presence of a fluorescent activator – is one of the most efficient chemiluminescence transformations known and widely utilized in analytical and bioanalytical applications. Coumarin derivatives have found widespread application as fluorescent labels for the determination of enzymatic activity in biological fluids and in fluorescence immunoassays, among others. In this work, we show that coumarin derivatives can be utilized as activators in the peroxyoxalate reaction (with two oxalic esters, including a new, environmentally compatible derivative) in anhydrous and aqueous systems, leading to reproducible kinetic results and singlet quantum yields similar to that obtained with commonly utilized activators. Quantum yields are lower in aqueous than in anhydrous medium, however still considerably high to allow the application in analytical and bioanalytical assays. The chemiluminescence parameters (singlet quantum yields at infinite activator concentration and relative electron transfer rate constants) determined in the systems indicate the occurrence of electron or charge transfer steps according to the Chemically Initiated Electron Exchange Luminescence (CIEEL) mechanism.



中文翻译:

在有机和水性介质中,香豆素衍生物在过氧草酸酯系统中用作活化剂

过氧草酸酯系统是草酸酯衍生物与过氧化氢在荧光活化剂存在下的碱催化反应,是已知的最有效的化学发光转化方法之一,已广泛用于分析和生物分析应用中。香豆素衍生物已被广泛地用作荧光标记,用于测定生物流体和荧光免疫测定等中的酶活性。在这项工作中,我们表明香豆素衍生物可在无水和水性体系中用作过氧草酸酯反应(与两种草酸酯,包括一种新的,环境相容的衍生物)一起用作活化剂,从而产生可再现的动力学结果和单重态量子产率,与之相似。用常用的活化剂获得。水溶液中的量子产率低于无水培养基中的量子产率,但是仍然很高,可以用于分析和生物分析。系统中确定的化学发光参数(在无限活化剂浓度下的单量子产率和相对的电子传输速率常数)指示根据化学引发的电子交换发光(CIEEL)机制发生的电子或电荷转移步骤。

更新日期:2021-01-07
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