超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法快速测定3种含生物碱类中药材中193种农药残留

A rapid screening method for 193 pesticide residues in 3 traditional Chinese medicines containing alkaloids by ultrahigh-performance liquid chromatography coupled to quadrupole-orbitrap high resolution mass spectrometry

基于超高效液相色谱-四极杆/静电场轨道阱高分辨质谱(UPLC-Q-Orbitrap HRMS)技术,建立了快速筛查和分析3种含生物碱类中药材(延胡索、黄连和黄柏)中193种农药残留的方法。样品经QuEChERS法提取,引入含阳离子交换型吸附剂的分散固相萃取净化,采用Agilent Poroshell 120 EC-C_(18)色谱柱(3.0 mm×150 mm,2.7μm)分离,以分别含有0.1%甲酸和5 mmol/L甲酸铵的水溶液和甲醇溶液作为流动相梯度洗脱,质谱采用全扫描/数据依赖的二级扫描模式(Full MS/ddMS2),外标法定量。结果显示:193种农药在相应的浓度范围内线性关系良好,相关系数(r)均在0.99以上;定量限为10~100μg/kg;在10、50、100μg/kg 3个添加水平下,延胡索、黄连和黄柏中193种农药的平均回收率分别为58%~120%、68%~124%和73%~122%,相对标准偏差(RSD)均在20%以内(n=6)。该方法前处理简便、快速,采用四极杆/静电场轨道阱高分辨质谱,通过母离子定量定性,二级碎片及保留时间定性,提高了含生物碱类中药材中农药残留筛查的准确度,可用于3种含生物碱类中药材中农药残留的快速筛查及日常风险监测。

A method for the fast screening and detection of 193 pesticide residues in 3 traditional Chinese medicines containing alkaloids was established based on ultrahigh-performance liquid chromatography coupled to quadrupole-orbitrap high resolution mass spectrometry(UPLC-Q-Orbitrap HRMS).The samples were extracted by QuEChERS method,cleaned up by dispersed solid phase extraction(d-SPE)with cation exchange adsorbents,and separated by Agilent Poroshell 120 EC-C_(18) column(3.0 mm×150 mm,2.7μm)with aqueous solution and methanol solution containing 0.1%formic acid and 5 mmol/L ammonium formate as mobile phase.Mass spectrometry adopted the full scan/data dependent acquisition mode(Full MS/ddMS2).External standard method was used for quantitative analysis.The results showed that 193 pesticides had good linear relationships within the corresponding concentration ranges,and the correlation coefficients(r)were all above 0.99,and the limits of quantification(LOQs)were 10-100μg/kg.At three different spiking levels of 10,50 and 100μg/kg,the average recoveries of 193 pesticides in Rhizoma Corydalis,Rhizoma Coptidis and Cortex Phellodendri were in the range of 58%-120%,68%-124%and 73%-122%,respectively,and the relative standard deviations(RSDs)were within 20%(n=6).The sample preparation of the established method is simple and rapid.Using the UPLC-Q-Orbitrap HRMS,through the quantitative and qualitative analysis of precursor ions and the qualitative confirmation of fragments ions and retention time,the screening accuracy of pesticide residues in traditional Chinese medicines containing alkaloids was significantly improved.It can be used for the rapid screening and daily risk monitoring of pesticide residues in the three traditional Chinese medicines containing alkaloids.