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手性超高效液相色谱串联质谱法在苯霜灵对映体分离及农作物对映体选择性降解过程研究中的应用

The application of chiral ultra-high-performance liquid chromatography tandem mass spectrometry to the separation of the zoxamide enantiomers and the study of enantioselective degradation process in agricultural plants.

作者信息

Pan Xinglu, Dong Fengshou, Chen Zenglong, Xu Jun, Liu Xingang, Wu Xiaohu, Zheng Yongquan

机构信息

State Key Laboratory for Biology of Plant Disease and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing, 100193, PR China.

State Key Laboratory for Biology of Plant Disease and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing, 100193, PR China.

出版信息

J Chromatogr A. 2017 Nov 24;1525:87-95. doi: 10.1016/j.chroma.2017.10.016. Epub 2017 Oct 6.

DOI:10.1016/j.chroma.2017.10.016
PMID:29030041
Abstract

In this study, an effective and sensitive chiral analytical method was developed to detect zoxamide enantiomers in vegetables, fruits and environmental matrices using ultra-high-performance liquid chromatography-tandem mass spectrometry. Optimal separation conditions were achieved with Lux Amylose-2 chiral column using acetonitrile/water (70:30v/v) as mobile phase with a flow rate and column temperature of 0.5mL/min and 25°C. The absolute configuration, optical rotation and elution order were confirmed for the first time. The average recoveries in all matrices at four spiking levels (0.5, 5, 50, 250μg/kg) ranged from 89.7 to 117.4%, with relative standard deviations being less than 10.9% for two enantiomers. The enantioselective dissipation of zoxamide in tomato showed that (-)-R-zoxamide was preferentially degraded leading to an enrichment of (+)-S-isomer, with half-lives of 3.80 d and 5.17 d, respectively. Inversely, (+)-S-zoxamide degraded faster than (-)-R-zoxamide in pepper (1.95day and 2.28day, respectively) and grape (2.03day and 2.87day). No significant enantioselectivity was observed in cucumber. The results of this study could help facilitate more accurate risk assessments of zoxamide in the future.

摘要

在本研究中,开发了一种高效灵敏的手性分析方法,用于使用超高效液相色谱 - 串联质谱法检测蔬菜、水果和环境基质中的唑菌胺酯对映体。使用Lux Amylose - 2手性柱,以乙腈/水(70:30 v/v)为流动相,流速为0.5 mL/min,柱温为25°C,实现了最佳分离条件。首次确认了绝对构型、旋光性和洗脱顺序。在四个加标水平(0.5、5、50、250μg/kg)下,所有基质中的平均回收率为89.7%至117.4%,两种对映体的相对标准偏差均小于10.9%。唑菌胺酯在番茄中的对映体选择性降解表明,(-)-R-唑菌胺酯优先降解,导致(+)-S-异构体富集,半衰期分别为3.80天和5.17天。相反,在辣椒(分别为1.95天和2.28天)和葡萄(分别为2.03天和2.87天)中,(+)-S-唑菌胺酯的降解速度比(-)-R-唑菌胺酯快。在黄瓜中未观察到明显的对映体选择性。本研究结果有助于在未来更准确地评估唑菌胺酯的风险。

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