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中性pH条件下亚硝胺和亚硝基酰胺的光解:一项自旋捕获研究。

Photolysis of nitrosamines and nitrosamides at neutral pH: a spin-trap study.

作者信息

Grover T A, Ramseyer J A, Piette L H

出版信息

Free Radic Biol Med. 1987;3(1):27-32. doi: 10.1016/0891-5849(87)90036-0.

DOI:10.1016/0891-5849(87)90036-0
PMID:3040536
Abstract

A model system has been used to study the types of radicals formed on denitrosation of N-nitroso compounds. Free radicals were formed at room temperature (22 degrees-23 degrees C) and neutral pH by photolytic cleavage of N-nitroso bonds and were partially characterized following their addition to the spin traps 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and N-tert-butyl-alpha-phenyl-nitrone (PBN). Carbon-centered radical adducts were obtained during nitrosamine photolysis and nitrogen-centered radical adducts during nitrosamide photolysis. Since both the nitrosamines and nitrosamides initially form nitrogen-centered radicals on photolysis, a secondary reaction or rearrangement must occur after initial N-nitroso bond cleavage in the nitrosamines. Mechanisms are proposed to account for these results.

摘要

一个模型系统已被用于研究N-亚硝基化合物脱亚硝基过程中形成的自由基类型。通过光解N-亚硝基键,在室温(22摄氏度至23摄氏度)和中性pH条件下形成自由基,并在它们加成到自旋捕获剂5,5-二甲基-1-吡咯啉-N-氧化物(DMPO)和N-叔丁基-α-苯基硝酮(PBN)后对其进行了部分表征。在亚硝胺光解过程中获得了以碳为中心的自由基加合物,在亚硝酰胺光解过程中获得了以氮为中心的自由基加合物。由于亚硝胺和亚硝酰胺在光解时最初都形成以氮为中心的自由基,因此在亚硝胺中初始N-亚硝基键断裂后必须发生二级反应或重排。提出了相应机制来解释这些结果。

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