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氰戊菊酯光解过程中产生的自由基的新型荧光检测

Novel fluorescence detection of free radicals generated in photolysis of fenvalerate.

作者信息

Suzuki Yusuke, Katagi Toshiyuki

机构信息

Environmental Health Science Laboratory, Sumitomo Chemical Co, Ltd, Takarazuka, Hyogo, Japan.

出版信息

J Agric Food Chem. 2008 Nov 26;56(22):10811-6. doi: 10.1021/jf802879q.

DOI:10.1021/jf802879q
PMID:18983159
Abstract

Photoinduced decarboxylation via homolytic cleavage of the ester linkage generating two benzyl radicals being recoupled is known to be a major photolytic pathway of the insecticide fenvalerate in aqueous or organic solvents. A highly sensitive and selective fluorescence spectroscopic method was applied to detect these radicals generated under xenon lamp irradiation in organic solvents and aqueous acetonitrile solutions. The short-lived radicals were efficiently trapped by the nitroxide free radical having a primary amino group, and the resultant diamagnetic adducts were instantaneously derivatized with fluorescamine as a fluorescent probe. The highly fluorescent derivatives were successfully separated and detected by a reversed-phase high-performance liquid chromatography equipped with a fluorescence detector, and their structures were individually identified by liquid chromatography/mass spectrometry.

摘要

通过酯键的均裂产生两个再耦合的苄基自由基的光诱导脱羧反应,已知是杀虫剂氰戊菊酯在水性或有机溶剂中的主要光解途径。应用一种高灵敏度和选择性的荧光光谱方法来检测在氙灯照射下在有机溶剂和乙腈水溶液中产生的这些自由基。具有伯氨基的氮氧自由基有效地捕获了这些短寿命自由基,所得的抗磁性加合物立即用荧光胺作为荧光探针进行衍生化。通过配备荧光检测器的反相高效液相色谱成功分离并检测了高荧光衍生物,并通过液相色谱/质谱分别鉴定了它们的结构。

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