分子印迹固相萃取-超高效液相色谱串联质谱法测定水产品中15种硝基咪唑类药物及其代谢物残留

Determination of 15 nitroimizadoles and their metabolites residues in aquatic products by MISPE-UPLC-MS/MS

建立了分子印迹固相萃取(MISPE)-超高效液相色谱串联质谱法(MISPE-UPLC-MS/MS)测定水产品中15种硝基咪唑类药物(NMZs)及其代谢物多残留分析方法。样品经乙酸乙酯提取,采用优化的MISPE条件富集净化。以甲醇和水作为流动相梯度洗脱,Kinetex C18色谱柱分离。电喷雾电离正离子(ESI+)模式扫描,多反应监测(MRM)模式测定,内标法定量。在质量浓度0.1~100 ng/mL范围内,各目标药物呈良好的线性关系,相关系数(r)≥0.998。方法的检出限(LOD)和定量限(LOQ)分别为0.1~0.3μg/kg和0.3~0.8μg/kg。阴性样品中平均加标回收率为83.6%~118%,相对标准偏差为2.7%~10%。该方法已应用于市售水产品基质中NMZs及其代谢物多残留测定。

A selective multi-residue method(MISPE-UPLC-MS/MS)was established by combining molecularly imprinted solid phase extraction(MISPE)cleanup with ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)for the residual determination of 15 nitroimizadoles(NMZs)and their metabolites in aquatic products.Samples were extracted with ethyl acetate and then purified by using optimized MISPE protocol prior to injection into UPLC-MS/MS.Chromatographic separation of 15 target analytes was performed on a Kinetex C18 column utilizing methanol and water as mobile phases under gradient elution procedure.These compounds were quantitated with internal standard method and confirmed in multiple reaction monitoring(MRM)mode using positive electrospray ionization(ESI+)scan.The linear ranges for 15 NMZs were 0.1-100 ng/mL with the coefficient of correlations(r)higher than 0.998.The limits of detection(LODs)and the limits of quantitation(LOQs)were in the range of 0.1-0.3μg/kg and 0.3-0.8μg/kg,respectively.The average spiked recoveries in negative sample ranged from 83.6%to 118%with the relative standard deviations(RSDs)of 2.7%-10%.The proposed method was successfully applied to the multi-residue determination of 15 NMZs and their metabolites in commercial aquatic sample matrixes with high selectivity and good applicability.