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首页> 外文期刊>Nucleic Acids Research >Structure-dependent reactivity of oxyfunctionalized acetophenones in the photooxidation of DNA: base oxidation and strand breaks through photolytic radical formation (spin trapping, EPR spectroscopy, transient kinetics) versus photosensitization (ele
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Structure-dependent reactivity of oxyfunctionalized acetophenones in the photooxidation of DNA: base oxidation and strand breaks through photolytic radical formation (spin trapping, EPR spectroscopy, transient kinetics) versus photosensitization (ele

机译:氧官能化的苯乙酮在DNA的光氧化中的结构依赖性反应性:通过光解自由基的形成(自旋捕集,EPR光谱,瞬态动力学)与光敏化(ele)进行碱基氧化和链断裂

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摘要

The photooxidative damage of DNA, specifically guanine oxidation and strand-break formation, by sidechain-oxyfunctionalized acetophenones (hydroxy, methoxy, tert-butoxy and acetoxy derivatives), has been examined. The involvement of triplet-excited ketones and their reactivity towards DNA has been determined by time-resolved laser-flash spectro-scopy. The generation of carbon-centered radical species upon Norrish-type I cleavage has been assessed by spin-trapping experiments with 5,5-dimethyl-1-pyrroline N-oxide, coupled with electron paramagnetic resonance spectroscopy. The observed DNA-base oxidation and strand-break formation is discussed in terms of the peroxyl radicals derived from the triplet-excited ketones by α cleavage and molecular oxygen trapping, as well as direct interaction of the excited states by electron transfer and hydrogen-atom abstraction. It is concluded that acetophenone derivatives, which produce radicals upon photolysis, in particular the hydroxy (AP-OH) and tert-butoxy (AP-O~tBu) derivatives, are more effective in oxidizing DNA.
机译:研究了侧链-氧官能化的苯乙酮(羟基,甲氧基,叔丁氧基和乙酰氧基衍生物)对DNA的光氧化损伤,特别是鸟嘌呤氧化和链断裂的形成。三重激发态酮的参与及其对DNA的反应性已通过时间分辨激光闪光光谱法确定。通过使用5,5-二甲基-1-吡咯啉N-氧化物与电子顺磁共振波谱的自旋俘获实验,评估了Norrish I型裂解后以碳为中心的自由基物种的产生。讨论了观察到的DNA碱基的氧化和链断裂的形成,讨论了三重激发的酮通过α裂解和分子氧陷阱衍生的过氧自由基,以及电子转移和氢原子激发态的直接相互作用。抽象。结论是在光解时产生自由基的苯乙酮衍生物,特别是羟基(AP-OH)和叔丁氧基(AP-O〜tBu)衍生物,在氧化DNA方面更有效。

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