Department of Molecular Biology and Genetics, Research Center Flakkebjerg, Aarhus University, Forsøgsvej 1, 4200 Slagelse, Denmark.
Department of Agroecology, Research Center Flakkebjerg, Aarhus University, Forsøgsvej 1, 4200 Slagelse, Denmark.
Molecules. 2019 Jul 5;24(13):2473. doi: 10.3390/molecules24132473.
Xenobiotic detoxification in plant as well as in animals has mostly been studied in relationship to the deactivation of the toxic residues of the compound that, surely for azoxystrobin, is represented by its β-methoxyacrylate portion. In maize roots treated for 96 h with azoxystrobin, the fungicide accumulated over time and detoxification compounds or conjugates appeared timewise. The main detoxified compound was the methyl ester hydrolysis product (azoxystrobin free acid, 390.14 /) thought to be inactive followed by the glutathione conjugated compounds identified as glutathione conjugate (711.21 /) and its derivative lacking the glycine residue from the GSH (654.19 /). The glycosylated form of azoxystrobin was also found (552.19 /) in a minor amount. The identification of these analytes was done by differential untargeted metabolomics analysis using Progenesis QI for label free spectral counting quantification and MS/MS confirmation of the compounds was carried out by either Data Independent Acquisition (DIA) and Data Dependent Acquisition (DDA) using high resolution LC-MS methods. Neutral loss scanning and comparison with MS/MS spectra of azoxystrobin by DDA and MSe confirmed the structures of these new azoxystrobin GSH conjugates.
植物和动物中的外来化合物解毒主要是研究化合物的有毒残留物的失活，对于肟菌酯来说，肯定是其β-甲氧基丙烯酸酯部分。在 96 小时内用肟菌酯处理的玉米根中，杀真菌剂随时间积累，解毒化合物或轭合物随时间出现。主要的解毒化合物是甲酯水解产物（肟菌酯游离酸，390.14 /），被认为是无效的，其次是谷胱甘肽轭合物，鉴定为谷胱甘肽轭合物（711.21 /）和其缺少 GSH 中甘氨酸残基的衍生物（654.19 /）。肟菌酯的糖基化形式也以少量存在。这些分析物的鉴定是通过使用 Progenesis QI 进行无标记光谱计数定量的差异非靶向代谢组学分析完成的，通过高分辨率 LC-MS 方法进行化合物的 MS/MS 确认采用了数据非依赖性采集（DIA）和数据依赖性采集（DDA）。中性丢失扫描并与 DDA 和 MSe 的肟菌酯 MS/MS 谱进行比较，确认了这些新的肟菌酯 GSH 轭合物的结构。
