分散固相萃取结合UPLC-MS/MS测定柑桔中青霉素G及其代谢物残留

Determination of Penicillin G and Its Metabolite Residues in Citrus by Ultra-high Performance Liquid Chromatography-Tandem Mass Spectrometry with Dispersive Solid-phase Extraction

建立了分散固相萃取结合超高效液相色谱-串联质谱(DSPE/UPLC-MS/MS)快速检测柑桔中青霉素G及其代谢物青霉二酸和去羧青霉噻唑酸的分析方法。样品经80%乙腈提取,十八烷基键合硅胶吸附剂(C_(18))净化。目标残留物经Acquity UPLC~?HSS T3色谱柱分离,以乙腈-0.1%甲酸溶液为流动相进行梯度洗脱,采用正离子多反应监测模式(MRM)检测,基质匹配标准曲线法定量。结果表明,3种目标分析物可在5 min内实现有效快速分离;在5～2 000μg/L质量浓度范围内线性关系良好(r^2≥0.998 1),方法检出限(LOD)为0.5～1μg/kg,定量下限(LOQ)为5～10μg/kg。在3个不同加标水平下,柑桔果肉、果皮和全果中的平均回收率为76.7%～107%,相对标准偏差(RSD)为1.3%～9.6%。该方法快速、简便、灵敏、准确,适用于柑桔中青霉素G及其两种代谢物残留的测定。

A rapid method was developed for the determination of penicillin G and its two metabolites (penillic acid and penilloic acid ) residues in citrus by dispersive solid-phase extraction/ultra-high performance liquid chromatography-tandem mass spectrometry (DSPE/UPLC-MS/MS ).The citrus samples were extracted with 80 % acetonitrile,then purified with C 18 .The analytes were separated on an Acquity UPLC^■ HSS T3 column with acetonitrile and 0.1 % formic acid solution as mobile phases by gradient elution,and finally detected by tandem mass spectrometry in positive ESI mode (ESI +).Identification and quantitation were performed by UPLC-MS/MS under multi-reaction monitoring (MRM ) mode and matrix-matched standard curve method,respectively.Results showed that three analytes could realize an effective and rapid separation within 5 min.There were good linear relationships for the analytes in the concentration range of 5-2 000 μg/L with their correlation coefficients ( r 2 ) not less than 0.998 1.The limits of detection (LOD ) and limits of quantitation (LOQ ) of the method were in the ranges of 0.5-1 μg/kg and 5-10 μg/kg,respectively.The spiked recoveries for penicillin G and its metabolites in blank citrus samples were in the range of 76.7 %-107 %,with relative standard deviations (RSD ) of 1.3 %-9.6 %.The method is rapid,simple,sensitive and accurate,and is suitable for the determination of penicillin G and its two metabolite residues in citrus.