【摘要】 目的建立一种快速、灵敏的鳝鱼中己二烯雌酚、己烯雌酚、雌酮、己烷雌酚、17α-雌二醇、17β-雌二醇、雌三醇、17α-炔雌醇和戊酸雌二醇等9种雌激素残留的固相萃取超快速液相色谱-串联质谱(UFLC-MS/MS)检测方法。方法鳝鱼样品经乙腈提取后,用Waters OasisHLB小柱进行净化,在Shim-pack XR-ODSⅡ色谱柱(100mm×2.0mm,2.2μm)上,以含0.04%(V/V)氨水的甲醇水溶液为流动相进行梯度洗脱分离,采用电喷雾(ESI)负离子多反应监测(MRM)模式进行质谱分析,采用同位素稀释法定量。结果各待测物在0.5～50.0μg/L范围内具有良好的线性,相关系数>0.998,在鳝鱼中的回收率为81.0%～110.0%,相对标准偏差(RSDs)在1.92%～8.24%之间,最低定量检出限(信噪比大于10)在0.07～0.4μg/kg范围。同时研究了这9种雌激素的二级质谱特征,阐释了其二级质谱裂解途径。结论建立的方法简便、快速、干扰少、特异性强,能准确测定包括差向异构体17α-雌二醇和17β-雌二醇在内的9种目标物,适用于鳝鱼中痕量雌激素残留的监测,也可用于其它鱼类中痕量雌激素残留的确证检测。更多还原

【Abstract】 Objective Developing a rapid and sensitive analytical method based on ultrafast liquid chromatography-tandem mass spectrometry(UFLC-MS/MS) with solid-phase extraction(SPE) for the simultaneous determination of nine estrogens(dienestrol,diethylstilbestrol,estrone,hexestrol,17-alpha-estradiol,17-beta-estradiol,estriol,17α-ethinylestradiol and estradiol valerate) in eel.Methods After the sample was extracted by acetonitrile and cleaned by Waters Oasis HLB solid-phase extraction cartridge,the UFLC separation was performed on a Shim-pack XR-ODSⅡ column(100mm×2.0mm,2.2μm) with a linear gradient elution program of methanol solution containing 0.04% ammonia(v/v) and 0.04% ammonia aqueous solution(v/v) as the mobile phase.Electrospray ionization was applied and operated in the negative multiple reaction monitoring(MRM) mode.The quantitation was used by isotope internal standard dilution technique.Results The results showed that the limits of quantitation(LOQs,S/N(10) were in the range of 0.07-0.4μg/kg,the calibration curves were in good linearities for the nine analytes in the range of 0.5-50.0μg/L with the correlative coefficients(r2) more than 0.998,the recoveries were between 81.0% and 110.0% with the relative standard deviations(RSDs) of 1.92%-8.24%.Additional,the mass spectra characterization of the nine estrogens was discussed and the fragmentation pathways were speculated.Conclusion The developed method is rapid,sensitive,specific and reproducible,and adapts not only to the simultaneous determination of the nine trace estrogens including the epimer of 17-alpha-estradiol and 17-beta-estradiol but also to the identified detection in other fish tissues.更多还原