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化学进展 2017, Vol. 29 Issue (9): 930-942 DOI: 10.7536/PC170503 前一篇   后一篇

• 综述 •

卤代芳烃化学发光的结构效应、分子机制及其应用

朱本占1,2*, 谢琳娜1,2, 沈忱1,2, 高慧颖1,2, 朱丽雅1, 毛莉1,2*   

  1. 1. 中国科学院生态环境研究中心 环境化学与生态毒理学国家重点实验室 北京 100085;
    2. 中国科学院大学 北京 100049
  • 收稿日期:2017-05-03 修回日期:2017-08-22 出版日期:2017-09-15 发布日期:2017-09-05
  • 通讯作者: 朱本占,e-mail:bzhu@rcees.ac.cn;毛莉,e-mail:limao@rcees.ac.cn E-mail:bzhu@rcees.ac.cn;limao@rcees.ac.cn
  • 基金资助:
    中国科学院战略性先导科技专项（B类）（No.XDB01020300）和国家自然科学基金项目（No.21321004，21477139，21577149）资助
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Chemiluminescence Generation from Haloaromatic Pollutants:Structure-Activity Relationship, Molecular Mechanism and Potential Applications

Benzhan Zhu1,2*, Linna Xie1,2, Chen Shen1,2, Huiying Gao1,2, Liya Zhu1, Li Mao1,2*   

  1. 1. State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China;
    2. University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2017-05-03 Revised:2017-08-22 Online:2017-09-15 Published:2017-09-05
  • Supported by:
    The work was supported by the Strategic Priority Research Program of CAS (B) (No. XDB01020300) and the National Natural Science Foundation of China (No.21321004, 21477139, 21577149).
卤代芳烃是一类在环境中广泛存在的化合物，因其可能导致人体及生态系统的潜在环境风险而被公众日益关注。最近，高级氧化过程作为一种“环境绿色友好”的技术被用于处理和降解这类难降解持久性有机污染物。我们先前意外发现，卤代醌的典型代表物四氯苯醌与过氧化氢反应不仅会生成·OH，还会产生专一依赖于·OH的两次化学发光。进一步研究发现，对产生·OH的高级氧化体系而言，不仅四氯苯醌的前体五氯酚和其他卤代酚能产生化学发光，其余所有经测试的卤代芳烃也能产生化学发光。在此基础上，对19种氯酚同系物产生化学发光的结构-效应关系进行了系统研究，结果发现：氯原子取代数目越多化学发光越强。有趣的是，氯酚的化学发光还与生成的氯代醌中间体以及半醌自由基呈良好相关性。基于上述结果，我们认为反应生成了某种醌中间体以及激发态多羰基产物，正是它们导致了化学发光。进而开发出一种快速灵敏的化学发光分析手段，不仅可检测和定量痕量的卤代芳烃，还可为预测其毒性以及实时监测降解动力学提供有用信息。
关键词： 卤代芳烃, 高级氧化, 化学发光, 羟基自由基, 卤代醌中间体, 半醌自由基, 结构-效应关系
The ubiquitous distribution of halogenated aromatic pollutants (XAr)coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes (AOPs) have been employed as an "environmental-green" technology for treatment and degradation of such recalcitrant and highly toxic XAr. During our study on the molecular mechanism of metal-independent hydroxyl radicals (·OH) production by halogenated quinones and H2O2, we unexpectedly find that an unprecedented·OH-dependent two-step intrinsic chemiluminescene (CL) can be produced by H2O2 and tetrachloro-p-benzoquinone, which is the major carcinogenic metabolite of the widely-used wood preservative pentachlorophenol. We further find that·OH-producing AOPs-mediated degradation of pentachlorophenol and all other XAr could produce intrinsic CL that is directly dependent on the formation of the extremely reactive·OH.A systematic structure-activity relationship study for all 19 chlorinated phenols demonstrates that the CL increases with an increasing number of chlorine-substitution in general. More interestingly, a relatively good correlation is noticed that not only between CL intensity and chlorinated quinoid intermediates, but also between CL emission and semiquinone radicals. Taken together, we propose that·OH-dependent formation of quinoid intermediates, quinone-1,2-dioxetane and electronically excited carbonyl species is responsible for this unusual intrinsic CL production.A rapid, sensitive, simple, and effective CL method has been developed to not only detect and measure trace amount of XAr in real environment, but also to provide useful information for predicting the toxicity or monitoring the degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on remediation of other halogenated persistent organic pollutants by AOPs.
Contents
1 Introduction
2 An·OH-dependent CL could be generated by carcinogenic polyhalogenated quinones and H2O2
2.1 The CL system of tetrachloro-1,4-benzoquinone (TCBQ) and H2O2
2.2 Possible light-emitting intermediates
2.3 Molecular mechanism for·OH-dependent CL generation
2.4 Other halogenated quinones could generate similar·OH-dependent CL
3 Intrinsic·OH-dependent CL could also be produced from degradation of pentachlorophenol (PCP) during advanced oxidation processes
3.1 An intrinsic CL emission from advanced oxidation of PCP by the classic Fenton system
3.2 The primary intermediates and ring-opening product
3.3 Possible molecular mechanism for CL emission during·OH-dependent PCP degradation
4 The structure-activity relationship study on the CL emission from the degradation of chlorinated phenols
4.1 Chlorinated phenols could generate CL during the·OH-generating AOPs
4.2 A good correlation between CL emission and the formation of chlorinated quinoid intermediates
4.3 Possible molecular basis for the correlation between CL emission and chlorinated phenols
4.4 A good correlation between CL emission and the formation of the chlorinated semiquinone radicals
4.5 Relatively good correlations between CL and the toxicity/degradation rate of chlorinated phenols
5 Other halogenated aromatic compounds could generate intrinsic CL during their advanced degradation by·OH-generating systems
6 Conclusion
Key words: halogenated aromatic compounds, advanced oxidation, chemiluminescence, hydroxyl radical, halogenated quinonid intermediates, semiquione radical, structure-activity relationship

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