Transformation and removal of bisphenol A from aqueous phase via peroxidase-mediated oxidative coupling reactions: Efficacy, products, and pathways
Transformation and removal of bisphenol A from aqueous phase via peroxidase-mediated oxidative coupling reactions: Efficacy, products, and pathways
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DOI：
10.1021/es050036x
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发表时间：
2005-08-15
影响因子：
11.4
通讯作者：
Weber, WJ
中科院分区：
文献类型：
--
作者：
Huang, QG;Weber, WJ
本文系统研究了由辣根过氧化物酶介导的氧化偶联在水相中转化和去除双酚A （BPA）的可行性和机理。结果表明，在hrp介导的氧化偶联反应中，BPA可有效转化为可沉淀的固体产物。利用LC/MS和GC/MS技术鉴定了13种反应中间体和产物，并借助从头算分子模拟，提出了详细的反应途径。假设两个双酚a自由基主要通过一个氧原子与另一个丙基取代的芳香碳原子的相互作用而偶联，然后消除异丙基酚碳正离子。所有检测到的中间体或产物都可以解释为双酚a与其他中间体或产物之间的偶联或取代反应。在低底物浓度下，反应的有效性是用一种涉及固相萃取的灵敏分析程序来证明的。结果表明，催化氧化偶联反应可能是雌激素酚类化合物的重要自然转化途径，并表明其作为去除水和废水中雌激素的有效手段的潜力。
A systematic investigation of the feasibility of and mechanisms for transformation and removal of bisphenol A (BPA) from aqueous phase via oxidative coupling mediated by horseradish peroxidase is described. It is demonstrated that BPA can be effectively transformed into precipitable solid products in HRP-mediated oxidative coupling reactions. A total of 13 reaction intermediates and products are identified using LC/MS and GC/MS techniques, and with the help of ab initio molecular modeling, detailed reaction pathways are proposed. It is postulated that two BPA radicals are coupled primarily by the interaction of an oxygen atom on one radical and propyl-substituted aromatic carbon atom on another, followed by elimination of an isopropylphenol carboncation. All intermediates or products detected can be interpreted as resulting from either coupling or substitution reactions between BPA and other intermediates or products. The efficacy of the reaction at low substrate concentrations is demonstrated using a sensitive analytical procedure involving solid-phase extractions. The results suggest that catalyzed oxidative coupling reactions may be important natural transformation pathways for estrogenic phenolic compounds and indicate their potential use as an efficient means for removal of estrogenicity from waters and wastewaters.