Bussy Ugo, Chung-Davidson Yu-Wen, Buchinger Tyler, Li Ke, Smith Scott A, Jones A Daniel, Li Weiming
Department of Fisheries and Wildlife, Michigan State University, 480 Wilson Rd, East Lansing, MI, 48824, USA.
RTSF Mass Spectrometry and Metabolomics Core, Michigan State University, Biochemistry Building, 603 Wilson Rd, East Lansing, MI, 48824, USA.
Anal Bioanal Chem. 2018 Feb;410(6):1749-1761. doi: 10.1007/s00216-017-0830-8. Epub 2017 Dec 28.
The sea lamprey (Petromyzon marinus) is a destructive invasive species in the Great Lakes that contributed to the collapse of native fish populations in the mid-1900s. 3-Trifluoromethyl-4-nitrophenol (TFM) is a selective pesticide that has been applied to sea lamprey infested tributaries of the Great Lakes to kill larvae since the 1960s and has reduced the populations by as much as 90%. However, the metabolism of TFM by sea lamprey and non-target species is not fully illuminated. Elucidation of TFM metabolism is critical for understanding its mode of action and possible environmental impact. Here, we describe the screening, identification, synthesis and structural characterization of TFM metabolites in livers from sea lamprey and three non-target species that differ in their ability to survive TFM exposure. We identified glucuronidation, sulfation, N-acetylation, glutathione conjugation, and aromatic nitro group reduction as potential detoxification mechanisms. Seven metabolites were synthesized for use as markers of TFM metabolism in fish. Quantitative H NMR was used to assay synthesized metabolite stock solutions that were then used as standard material to develop a quantitative LC-MS/MS method for TFM metabolites.
海七鳃鳗（Petromyzon marinus）是五大湖地区具有破坏性的入侵物种，在20世纪中叶导致了当地鱼类种群的崩溃。自20世纪60年代以来，3-三氟甲基-4-硝基苯酚（TFM）一直作为一种选择性杀虫剂，被应用于五大湖受海七鳃鳗侵扰的支流，以杀死其幼虫，使海七鳃鳗种群数量减少了多达90%。然而，海七鳃鳗和非目标物种对TFM的代谢情况尚未完全明晰。阐明TFM的代谢对于理解其作用方式和可能的环境影响至关重要。在此，我们描述了在海七鳃鳗以及三种对TFM暴露的存活能力不同的非目标物种的肝脏中，对TFM代谢物的筛选、鉴定、合成及结构表征。我们确定了葡萄糖醛酸化、硫酸化、N-乙酰化、谷胱甘肽结合以及芳香硝基还原作为潜在的解毒机制。合成了七种代谢物，用作鱼类中TFM代谢的标志物。使用定量核磁共振氢谱对合成的代谢物储备溶液进行分析，然后将其用作标准物质，以开发一种针对TFM代谢物的定量液相色谱-串联质谱方法。
