目的：以加味逍遥片及其处方中的 6 种药材,2 种提取物作为研究对象,对其中 231 种农药残留情况进行检测,为加味逍遥片中农药残留情况研究及限度制定提供参考依据。方法：以《欧洲药典》规定的植物药中农药检测指标结合我国农药实际使用调研,共筛选出 231 个农药品种作为本方法的检测对象。对前处理方式进行考察和优化,针对加味逍遥片生产过程中涉及药材、中间体提取物及成药不同基质特点,确定了 6 种中药材,2 种提取物和 1 种制剂的前处理方法,样品采用乙腈匀浆提取,分散固相萃取法净化,在串联质谱多反应监测模式（MRM）下测定。 GC-MS/MS 和 LC-MS/MS 方法皆采用基质匹配标液计算残留量。结果：建立的 GC-MS/MS 和 LC-MS/MS 农药多残留检测法,各待测化合物质量浓度在 1.0~100.0 ng·mL-1 范围内呈线性良好,相关系数 r>0.99,在 0.01、0.1、0.5 mg·kg-1 三水平进行加样回收率考察,94% 的农药指标平均回收率在 70%~120% 之间,RSD ≤ 7%,符合痕量残留分析的检 测要求。采用建立的方法对药材、提取物和制剂共计 36 批次样品进行检测,共检出 12 种农药,但检出浓度水平较 低,除 1 批白芍中检出的七氯（0.34 mg·kg-1）超出《欧洲药典》限量规定（0.05 mg·kg-1）外,绝大部分符合限量标准的要求。结论：本研究建立了加味逍遥片及其处方中药材的农药多残留检测方法,此方法灵敏度高,准确、快速,且检测指标针对性强,可用于其日常生产全过程农药残留的监控。同时,检测结果为其农药风险防控提供理论参考。
Objective：To provide a reference for the research on limit formulation of pesticide residues in Jiawei Xiaoyao pills, the Jiawei Xiaoyao pills and 6 medicinal materials and 2 extracts in the prescription were taken as research objects, and 231 kinds of pesticide residue were detected. Methods：According to the actual use of pesticides in planting,and combining with the pesticide indicators to be tested in herbal medicines specified in the European Pharmacopoeia,231 pesticide residues were selected as the test indicators for this method,and then. According to the characteristics of different bases of Jiawei Xiaoyao pills,medicinal materials and extracts,the pretreatment methods for 6 Chinese medicinal material,2 extracts and the preparation were optimized. The samples were extracted by acetonitrile homogenate, clean-up by dispersive solid phase extraction, and determined by multi reaction monitoring mode（MRM）of tandem mass spectrometry. Both GC-MS/ MS and LC-MS/MS methods used matrix matching standard solution to calculate the residue. Results：The established GC-MS/MS and LC-MS/MS pesticide multi-residue detection methods,were linear in the range of 1.0-100.0 ng·mL-1 with correlation coefficients above 0.99. For 94% compunds,the average recoveries at spiked 3 levels（0.01,0.1 and 0.5 mg·kg-1）were 70%-120% with RSDs ≤ 7%,all meeting the requirements for trace pesticide residue detection. Using established methods,36 batches of samples of medicinal materials, extracts and preparation were detected,and 12 pesticides were detected. The concentrations were low,except for 0.34 mg·kg-1 of heptachlor detected in 1 batch of Paeoniae Radix Alba exceeding the the limit of 0.05 mg·kg-1 in the European Pharmacopoeia. The rest detected pesticides met the requirements of the limit standard. Conclusion：This study establishes a pesticide multi-residue detection method for Jiawei Xiaoyao pills and its Chinese herbal medicines. It is verified that this method had high sensitivity,accuracy,rapidity,and strong detection indicators. This method can be used for the monitoring of pesticide residues in its daily production,and the detection data provides a theoretical reference for its pesticide risk prevention and control.
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