Wen Qi, Smitha U Nair, David I Pattison, Robert F Anderson
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引用次数: 0
摘要
研究发现,一系列八种亚硝基化合物(四种取代的哌啶、三种吡咯烷和一种氧化哌啶)可与 2'-deoxyribose-peroxyl 和鸟苷自由基发生电子转移。根据常见的氧化还原指示剂氯丙嗪,测量了硝基化合物到氧氨阳离子的单电子氧化电位(氧氨还原电位)E0',发现其范围在 751 ± 15 mV 到 973 ± 15 mV 之间。在含氧水溶液中,2'-脱氧核糖-过氧自由基快速化学还原为过氧化氢(由-OH 自由基攻击 2-脱氧核糖 dR 生成)是一种氧化还原依赖反应,其速率常数为 0.8-3.5 x 107 M-1 s-1。亚硒酸根(SeO3--)单电子氧化 2'-deoxyguanosine monophosphate(dG)时产生的鸟苷自由基与亚硝基发生氧化还原依赖性反应,扩散速率常数为 1-2 x 108 M-1 s-1。这些发现表明,在 DNA 自由基的快速化学修复过程中,硝基氧化物可能起到了抗氧化作用,利用质粒进行的体外链断裂研究也证实了这一点。
Redox factors in the antioxidant activity of nitroxides toward DNA guanyl and 2-deoxyribose-peroxyl radicals.
A series of eight nitroxide compounds (four substituted piperidines, three pyrrolidines and one oxo-piperidine) are found to undergo electron transfer to 2'-deoxyribose-peroxyl and the guanyl radical. One-electron oxidation potentials of the nitroxides to oxoammonium cations (oxoammonium reduction potential), E0', have been measured against a common redox indicator, chlorpromazine, and found to span the range 751 ± 15 mV to 973 ± 15 mV. Fast chemical reduction of the 2'-deoxyribose-peroxyl radical to the hydroperoxide, generated by •OH radical attack on 2-deoxyribose, dR, in oxygenated aqueous solution, is a redox-dependent reaction, with rate constants of 0.8-3.5 x 107 M-1 s-1.The guanyl radicals, produced upon one-electron oxidation of 2'-deoxyguanosine monophosphate, dG, by the selenite radical, SeO3•-, react with the nitroxides in a redox-independent reaction with diffusion rate constants of 1-2 x 108 M-1 s-1. These findings represent a possible antioxidant role for nitroxides in the fast chemical repair of DNA radicals, which is supported by an in vitro strand break study using a plasmid.
期刊介绍:
Free Radical Research publishes high-quality research papers, hypotheses and reviews in free radicals and other reactive species in biological, clinical, environmental and other systems; redox signalling; antioxidants, including diet-derived antioxidants and other relevant aspects of human nutrition; and oxidative damage, mechanisms and measurement.