State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People's Republic of China.
Proc Natl Acad Sci U S A. 2012 Oct 2;109(40):16046-51. doi: 10.1073/pnas.1204479109. Epub 2012 Sep 17.
Most chemiluminescence (CL) reactions usually generate only one-step CL, which is rarely dependent on the highly reactive and biologically/environmentally important hydroxyl radicals ((•)OH). Here, we show that an unprecedented two-step CL can be produced by the carcinogenic tetrachloro-1,4-benzoquinone (also known as p-chloranil) and H(2)O(2), which was found to be well-correlated to and directly dependent on its two-step metal-independent production of (•)OH. We proposed that (•)OH-dependent formation of quinone-dioxetane and electronically excited carbonyl species might be responsible for this unusual two-step CL production by tetrachloro-1,4-benzoquinone/H(2)O(2). This is a unique report of a previously undefined two-step CL-producing system that is dependent on intrinsically formed (•)OH. These findings may have potential applications in detecting and quantifying (•)OH and the ubiquitous polyhalogenated aromatic carcinogens, which may have broad biological and environmental implications for future research on these types of important species.
大多数化学发光(CL)反应通常只产生一步 CL,很少依赖于高反应性和生物/环境重要的羟基自由基((•)OH)。在这里,我们表明,致癌的四氯-1,4-苯醌(也称为对氯苯醌)和 H(2)O(2)可以产生前所未有的两步 CL,这被发现与它的两步非金属依赖性(•)OH 生成密切相关,并直接依赖于此。我们提出,(•)OH 依赖性醌二氧杂环己烷和电子激发的羰基物种的形成可能是四氯-1,4-苯醌/H(2)O(2)产生这种不寻常两步 CL 的原因。这是一个以前未定义的两步 CL 产生系统的独特报告,该系统依赖于内在形成的(•)OH。这些发现可能在检测和量化(•)OH 和普遍存在的多卤代芳香致癌物质方面具有应用潜力,这可能对未来研究这些重要物质类型具有广泛的生物学和环境意义。