固相萃取-高效液相色谱串联质谱法同时测定鱼子酱中12种磺胺类药物残留

Simultaneous determination of 12 sulfonamides residues in caviar by solid phase extraction-high performance liquid chromatography tandem mass spectrometry

首次建立了一种同时测定鱼子酱中磺胺嘧啶、磺胺二甲基嘧啶、磺胺二甲基异恶唑和磺胺间甲氧嘧啶等12种磺胺类药物残留的固相萃取-高效液相色谱-串联质谱分析方法。根据鱼子酱脂溶性的特点,试样采用正己烷溶剂预溶解,用乙酸乙酯提取2次后经混合型阳离子交换固相萃取柱(MCX)净化,用InertSustain Swift C_(18)柱(150 mm×4.6 mm,5μm)分离,多反应监测(MRM)模式串联质谱进行测定,以内标法定量。结果显示,磺胺类药物在1.00~20.00 ng/mL范围内12种测定物均具有较好的线性关系,相关系数均≥0.99,方法定量限(S/N>10)为1.0μg/kg。对阴性鱼子酱在3个添加水平下(1.0μg/kg、2.0μg/kg和5.0μg/kg)分别进行加标回收试验,实际样品中12种测定物质的平均回收率在72.9%~119.0%之间,相对标准偏差(RSD,n=6)在0.9%~11.0%之间。应用本方法对2018—2020年采集的320个鱼子酱样品进行检测,结果表明均为未检出磺胺类药物残留。本方法快速、灵敏、准确,适用于日常大批量鱼子酱样品中磺胺类药物及其代谢物残留的定性、定量分析。

First establish a solid phase extraction(SPE)-high performance liquid chromatography(HPLC)-tandem mass spectrometry method for the simultaneous determination of sulfadiazine,sulfamethazine,sulfadimethyl Isoxazole and sulfamonomethoxine residues in Caviar.According to the fat soluble characteristics of Caviar,the sample was pre dissolved with n-hexane solvent,extracted twice with ethyl acetate,purified with mixed cation exchange solid phase extraction column(MCX),and separate with InertSustain Swift C_(18) column(150 mm×4.6 mm,5μm),multi reaction monitoring(MRM)mode tandem mass spectrometry for determination,internal standard method for quantification.The results showed that there was a good linear relationship between the 12 analytes of sulfonamide drugs in the range of 1.00-20.00 ng/mL,with a correlation coefficient greater than 0.99,and a method quantification limit(S/N>10)of 1.0μg/kg.For negative Caviar,at 3 addition levels(1.0μg/kg,2.0μg/kg and 5.0μg/kg)were subjected to spiked recovery tests,and the average recovery rates of the 12 measured substances in the actual samples ranged from 72.9%to 119.0%,with a relative standard deviation(RSD,n=6)is between 0.9%and 11%.This method was used to detect 320 Caviar samples from 2018 to 2020,and the results showed that no sulfonamides residues were detected.This method is rapid,sensitive and accurate,and is suitable for qualitative and quantitative analysis of sulfonamides and their metabolites residues in daily mass Caviar samples.