QuEChERS-超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法同时测定生姜中21种喹诺酮类抗生素残留

Simultaneous determination of 21 kinds of quinolone antibiotic residues in gingers by QuEChERS-ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry

目的建立QuEChERS-超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法(ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high re solution mas s spectrometry,UPL C-Q Orbitrap HRMS)同时测定生姜中21种喹诺酮类抗生素的分析方法。方法生姜样品采用3%乙酸乙腈、8 g无水硫酸钠提取,150 mg乙二胺-N-丙基硅烷化硅胶(primary secondary amine,PSA)和1.5 g无水硫酸钠净化。目标分析物以乙腈和0.1%甲酸水溶液为流动相,经Phenomenex Kinetex F5(100 mm×2.1 mm,2.6μm)色谱柱分离,在正离子模式下采用全扫描和自动触发二级质谱模式采集方式,外标法定量。结果生姜中21种喹诺酮类抗生素在0.001~0.500μg/mL间呈现良好的线性关系,相关系数(r;)在0.9939-0.9993之间,方法定量限为0.1~1.0μg/kg。在10、20、40μg/kg3个浓度水平下进行加标回收实验,平均回收率为71.3%~106.7%,相对标准偏差为0.6%-8.9%。除氟甲喹外,生姜中喹诺酮类抗生素均为基质抑制效应。该方法用于43个生姜样品中喹诺酮类抗生素检测,均未检出。结论该方法适用于生姜中21种喹诺酮类抗生素残留的快速筛查和定量测定,但在低含量无法获取二级离子的情况下需辅助平行反应监测(parallel reaction monitoring,PRM)扫描模式进行确证,以避免假阳性情况的发生。

Objective To establish a method for the simultaneous determination of 21 kinds of quinolone antibiotic in gingers by QuEChERS-ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry.Methods Ginger samples were extracted by acetonitrile containing 3% acetic acid,8 g anhydrous sodium sulfate,purified with 150 mg primary secondary amine(PSA)and 1.5 g anhydrous sodium sulfate.The extact separated on Phenomenex Kinetex F5(100 mm×2.1 mm,2.6μm),acetonitrile-0.1% formic acid was used as the mobile phase.The compounds were detected by full scan/data-dependent MS;(Full MS/dd-MS;)under positive ion mode and quantified by the external standard method.Results Good linearities were obtained for 21 kinds of quinolones in the concentration range of 0.001-0.500μg/mL with the correlation coefficients(r;)of 0.9939-0.9993,and the limits of quantitation of ranged from 0.1 to 1.0μg/kg.Recoveries were in the range of 71.3% to 106.7% with relative standard deviations of 0.6%-8.9% at spiked levels of 10,20,40μg/kg.The matrix effects were negative in most of cases,except flumequine.The method was applied to the determination of quinolones in 43 ginger samples,and none was detected.Conclusion This method is suitable for rapid screening and quantitative determination of 21 kinds of quinolone antibiotic residues in gingers.However,it needs to be confirmed by parallel reaction monitoring(PRM)scanning mode to avoid false positive when the secondary daughter ions cannot be obtained at low content.