卤代醌是许多卤芳香持久有机污染物的致癌代谢产物和饮用水消毒副产物。羟基自由基(OH)被公认为生物系统中最具活性的活性氧物种,能导致生物体内DNA等生物大分子的氧化损伤。目前,最被广泛接受的0H产生机理是过渡金属离子催化的Fenton反应。综合采用电子自旋共振二级自旋捕获和其他分析方法,发现四氯苯醌和其它卤代醌皆可通过不依赖于过渡金属离子的途径,显著促进氢过氧化物(H2O2或有机氢过氧化物)的分解而产生OH或烷氧自由基,并首次检测到一种新型的、以碳为中心的醌自由基。基于以上研究,提出一类不依赖于过渡金属离子的卤代醌介导的新型有机类Fenton反应机理。
Halogenated quinones are a class of carcinogenic metabolites of many halogenated persistent organic pollutants and new chlorination disinfection byproducts in drinking water. The hydroxyl radical (OH) has been considered to be one of the most reactive oxygen species produced in biological systems. It has been shown that OH can cause oxidative damage to DNA and other macromolecules. One of the most widely accepted mechanisms for OH production is through the transition metal-catalyzed Fenton reaction. Through the complementary application of electron spin resonance (ESR) secondary spin-trapping and other analytical methods, we found that tetrachloro-1,4-benzoquinone (TCBQ) and other halogenated quinones could markedly enhance the decomposition of hydroperoxides (H2O2 and organic hydroperoxides) and formation of "OH and alkoxyl radicals independent of transition metal ions. A novel carbon-centered quinone ketoxy radical was also detected and identified for the first time. Based on these data, we proposed a novel mechanism for metal-independent and halogenated quinone-mediated organic Fenton-like reaction.