Degradation andmetabolic profiling for benzene kresoxim-methyl using carbon-14 tracing
Degradation andmetabolic profiling for benzene kresoxim-methyl using carbon-14 tracing
复制标题
使用碳 14 示踪对苯醚菌酯进行降解和代谢分析
DOI：
10.1016/j.scitotenv.2018.05.123
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发表时间：
2018
影响因子：
9.8
通讯作者：
Wang Wei
中科院分区：
文献类型：
--
作者：
Wang Likun;Zhao Jinhao;Delgado-Moreno Laura;Cheng Jingli;Wang Yichen;Zhang Sufen;Ye Qingfu;Wang Wei
甲基苯甲苯(BKM)是一种防治真菌病原菌的有效杀菌剂，但对其降解代谢的研究较少。本研究采用~(14)C示踪和高效液相色谱-飞行时间-质谱联用技术研究了BKM在土壤中的降解和代谢规律。结果表明，100 天后，有88%~98%的14C-BKM仍以母体或不完全中间体的形式存在。观察到3种主要放射性代谢物(M1~M3，≥90%)和3种从属放射性代谢物(mA~Mc，≤2%)，以及1种非放射性代谢物M4。主要中间体通过自身合成其真实标准进一步得到确认，并提出了BKM的降解途径，包括：1)丙烯酸酯双键的氧化裂解得到BKM-烯醇(M1)；2)甲酯水解得到BKM酸(M2)；3)M1和M2裂解得到Mc，Mc可以脱羧基得到M3；以及4)芳环之间的乙醚裂解形成M4。本研究通过首次揭示BKM的转化途径，建立了一种稳定的Strobilurins代谢谱方法，并对BKM的最终命运有了更深入的了解，这可能也有助于理解其他类似的Strobilurins的风险。
Benzene kresoxim-methyl (BKM) is an effective strobilurin fungicide for controlling fungal pathogens but limited information is available on its degradation and metabolism. This study explored the degradation and metabolic profiling for BKM in soils by carbon-14 tracing and HPLC-TOF-MS2analyzing. Results indicated that 88%–98% of14C-BKM remained as parent or incomplete intermediates after 100 days. Three main radioactive metabolites (M1 to M3, ≥90%) and three subordinate radioactive metabolites (Ma to Mc, ≤2%) were observed, along with a non-radioactive metabolite M4. The main intermediates were further confirmed by self-synthesizing their authentic standards, and BKM was proposed to degrade via pathways including: 1) the oxidative cleavage of the acrylate double bond to give BKM-enol (M1); 2) the hydrolysis of the methyl ester to give BKM acid (M2); 3) the cleavage of M1 and M2 to yield Mc, which could be decarboxylated to give M3; and 4) the ether cleavage between aromatic rings to form M4. This study builds a solid metabolic profiling method for strobilurins and gives a deeper insight into the eventual fate of BKM by demonstrating its transformation pathways for the first time, which may also be beneficial for understanding the risks of other analogous strobilurins.