基于改进QuEChERS法联合超高效液相色谱-质谱法的人参中禁用农药残留分析

Modified QuEChERS Combined with UPLC-MS/MS for Analysis of Banned Pesticide Residues in Ginseng Radix et Rhizoma

目的:以人参中禁用农药残留分析为例对QuEChERS法进行改进,为中药禁用农药残留分析提供参考。方法:用超高效液相色谱-质谱法(UPLC-MS/MS)多反应监测模式(MRM)对人参中30种禁用农药残留进行检测,对净化剂硅胶、十八烷基键合硅胶(C_(18))、N-丙基乙二胺(PSA)、石墨化碳黑(GCB)的种类及用量进行优化,考察方法回收率、精密度、线性和定量限。结果:过量的硅胶和C_(18)会造成杀虫脒回收率降低,PSA会造成酸性农药如甲磺隆、氯磺隆、胺苯磺隆回收率降低。当硅胶、C_(18)和PSA用量为100~150 mg时,所有农药均有较好的回收率。以硅胶、C_(18)、PSA和GCB用量分别为100、150、150、90 mg为例,30种农药的加样回收率为76.4%~108.0%,精密度相对标准偏差(RSD)为0.9%~7.8%,线性相关系数(r)为0.9939~0.9999,定量下限(LLOQ)均低于《中华人民共和国药典》2020年版规定。结论:经过净化剂用量调整后,改进的QuEChERS法有较好的准确度、精密度、线性和定量限,可以用于人参等中药中禁用农药残留分析。

Objective:To modify QuEChERS method and provide references for the analysis of banned pesticide residues in Chinese medicine,with Ginseng Radix et Rhizoma as an example.Methods:The residues of 30 banned pesticides in ginseng were detected by ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)in multi-reaction monitoring mode(MRM).The types and dosages of purifiers silica gel,octadecyl-bonded silica gel(C_(18)),Npropyl ethylenediamine(PSA),and graphitized carbon black(GCB)were optimized.The recovery rate,precision,linearity,and limit of quantification of the method were investigated.Results:Excessive silica gel and C_(18) reduced the recovery rate of chlordimeform,and PSA reduced the recovery rate of acid pesticides such as metsulfuron-methyl,chlorsulfuron,and ethametsulfuron.When the dosage of silica gel,C_(18),and PSA was 100-150 mg,all pesticides had good recovery rates.For example,when the dosage of silica gel,C_(18),PSA,and GCB was 100,150,150,and 90 mg,respectively,the recovery rates of 30 pesticides were 76.4%-108.0%,relative standard deviation(RSD)was 0.9%-7.8%,and the linear correlation coefficients(r)were 0.9939-0.9999.The lower limits of quantification(LLOQ)of all pesticides were lower than the limits of quantification(LOQ)in the Chinese Pharmacopoeia(2020 edition).Conclusion:After adjusting the dosage of purifiers,the modified QuEChERS method has good accuracy,precision,linearity,and LOQ,which can be used for the analysis of banned pesticide residues in Ginseng Radix et Rhizoma and other Chinese medicine.