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采用简化前处理和 UFLC-ESI-MS/MS 法测定中药材中多种类型的三嗪类除草剂及其代谢物。

Determination of triazine herbicides and their metabolites in multiple medicinal parts of traditional Chinese medicines using streamlined pretreatment and UFLC-ESI-MS/MS.

机构信息

Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences, Peking Union Medical College, Beijing, 100193, China.

Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences, Peking Union Medical College, Beijing, 100193, China; College of Traditional Chinese Medicine, Jilin Agricultural University, Changchun, 130118, China.

出版信息

Chemosphere. 2018 Jan;190:103-113. doi: 10.1016/j.chemosphere.2017.09.085. Epub 2017 Sep 18.

Abstract

A rapid, sensitive, and reliable ultra-fast liquid chromatography combined with electrospray ionization tandem mass spectrometry (UFLC-ESI-MS/MS) method was established and applied to simultaneous determination of 31 triazine herbicides and their metabolites in multiple medicinal parts of traditional Chinese medicines (TCMs). A streamlined pretreatment approach using one-step extraction and dilution was proposed, which provided high-throughput processing, excellent recovery, and negligible interference. Afterwards, multiple-reaction monitoring (MRM) and information-dependent acquisition (IDA) triggered enhanced product ion spectra (EPI) was adopted to identify and quantify the targets in a single analysis. The optimized method was then validated according to the guidelines of the European Commission for the following parameters: Matrix effects, specificity, accuracy, precision, linearity, range, and stability. The LOD and LOQ for the 31 triazine herbicides were 0.1-10 μg kg and 0.5-25 μg kg, respectively. Recoveries at three concentration levels were within 67.9-120.3% with an associated precision RSD <20%. Using the proposed approach, trazines herbicides were determined from 44 commercially available TCMs. The detection rate of triazine herbicides residues was 15.9% of the total samples. Among them, atrazine, simeton, and simetryn were found in the radix, herba, and seed TCMs with values far below the referenced maximum residue limits (MRLs), but no residues were detected in either the flos or fructus. Taken together, this method has the potential to provide a means for triazines screening in extensive matrices, thereby laying the foundation for pesticide registration on TCMs. Moreover, it has the potential to guide further triazine residue control in TCMs.

摘要

建立了一种快速、灵敏、可靠的超高效液相色谱-电喷雾串联质谱(UFLC-ESI-MS/MS)方法,用于同时测定中药多个药用部位的 31 种三嗪类除草剂及其代谢物。提出了一种一步提取和稀释的流线型预处理方法,该方法具有高通量处理、高回收率和可忽略的干扰。随后,采用多反应监测(MRM)和信息相关采集(IDA)触发增强产物离子谱(EPI),在单次分析中对目标物进行鉴定和定量。然后,根据欧盟委员会的指南对优化后的方法进行验证,参数包括基质效应、特异性、准确度、精密度、线性、范围和稳定性。31 种三嗪类除草剂的检出限和定量限分别为 0.1-10μg/kg 和 0.5-25μg/kg。在三个浓度水平下的回收率在 67.9-120.3%之间,相关精密度 RSD<20%。使用所提出的方法,从 44 种市售中药中检测到了三嗪类除草剂。三嗪类除草剂残留的检出率为总样品的 15.9%。其中,莠去津、西玛津和西草净在根、草和种子类中药中被检出,其值远低于参考最大残留限量(MRLs),但在花和果实中均未检出残留。综上所述,该方法有可能为广泛基质中的三嗪类筛查提供一种手段,从而为中药的农药登记奠定基础。此外,它还有可能指导进一步控制中药中的三嗪类残留。

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