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CF3O2.、CCl3O2.和CBr3O2.自由基在水溶液中进行单电子氧化的速率常数。

Rate constants for one-electron oxidation by the CF3O2., CCl3O2., and CBr3O2. radicals in aqueous solutions.

作者信息

Huie R E, Brault D, Neta P

出版信息

Chem Biol Interact. 1987;62(3):227-35. doi: 10.1016/0009-2797(87)90024-x.

DOI:10.1016/0009-2797(87)90024-x
PMID:3621370
Abstract

The peroxyl radicals CF3O2., CCl3O2. and CBr3O2. were produced by radiolysis of aerated aqueous-alcohol solutions of CF3Br, CF3Cl, CCl4 or CBr4. Kinetic spectrophotometric pulse radiolysis experiments were carried out in the presence of various substrates: urate, ascorbate, xanthine, hydroquinone, p-methoxyphenol, phenol and chlorpromazine. Absolute rate constants for one-electron oxidation of these substrates by the alkylperoxyl radicals were found to vary from less than 10(5) to greater than 10(9) M-1 s-1, depending to some extent on the redox potential of the substrate. For all substrates the order of reactivity was CF3O2. greater than CBr3O2. greater than CCl3O2. . Because of its high reactivity, CF3O2., may have deleterious effects on biological systems. Its likely environmental precursor, CF3Br, which is used as a fire extinguisher and a refrigerant, was found to be reduced by a ferrous porphyrin model for cytochrome P-450 only very slowly and thus is not expected to have a major toxic effect if inhaled.

摘要

过氧自由基CF3O2.、CCl3O2.和CBr3O2.是通过对CF3Br、CF3Cl、CCl4或CBr4的充气醇水溶液进行辐射分解产生的。动力学分光光度脉冲辐射分解实验是在各种底物存在的情况下进行的:尿酸盐、抗坏血酸盐、黄嘌呤、对苯二酚、对甲氧基苯酚、苯酚和氯丙嗪。发现这些底物被烷基过氧自由基单电子氧化的绝对速率常数从小于10(5)到大于10(9) M-1 s-1不等,在一定程度上取决于底物的氧化还原电位。对于所有底物,反应活性顺序为CF3O2.大于CBr3O2.大于CCl3O2.。由于其高反应活性,CF3O2.可能对生物系统产生有害影响。它可能的环境前体CF3Br用作灭火器和制冷剂,发现它被细胞色素P-450的亚铁卟啉模型还原得非常缓慢,因此如果吸入预计不会产生重大毒性作用。

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