EMR固相萃取-超高效液相色谱-串联质谱法测定虾肉中性激素残留的方法建立

本研究建立EMR固相萃取结合超高效液相色谱-串联质谱测定虾肉中15种性激素残留的分析方法。样品采用0.1 mol/L乙二胺四乙酸二钠溶液-乙腈溶液提取，经Captiva EMR固相萃取SPE小柱净化，CAPCELLPAK C₁₈ BB-H（3 μm，2.1 mm×150 mm）色谱柱分离，电喷雾离子源正负离子分开扫描；多反应监测模式的超高效液相色谱-串联质联质谱法进行检测，以空白基质匹配外标法定量。正离子流动相为甲醇和0.1%甲酸，检测雄激素与孕激素；负离子流动相为乙腈和0.01%氨水溶液，检测雌激素。结果表明，经EMR固相萃取净化的虾肉样品中的15种性激素残留在1～50 μg/kg浓度范围内线性关系良好，相关系数（r）均大于0.99，方法检出限为0.0015～0.436 μg/kg，定量限为0.0051～1.453 μg/kg，平均回收率在85.31%~119.84%，相对标准偏差为2.11%~9.86%（n=6）。本方法操作快速简单，重复性好，灵敏度较高，适用于虾肉中15种性激素残留的检测。

Determination of Sex Hormone Residues in Shrimp by EMR Solid Phase Extraction-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

A method for the determination of 15 sex hormones in shrimp meat by EMR solid phase extraction combined with ultra performance liquid chromatography-tandem mass spectrometry was established. The samples was extracted with 0.1 mol/L ethylenediaminetetraacetic acid disodium solution and acetonitrile solution, purified by Captiva EMR SPE cartridge, separated by CAPCELLPAK C₁₈ BB-H (3 μm, 2.1 mm×150 mm) column, and scanned by positive and negative ions of electrospray ion source. Ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with multiple reaction monitoring mode was used for detection, and blank matrix matching external standard method was used for quantification. The positive ion mobile phase was methanol and 0.1% formic acid, and androgen and progesterone were detected. The negative ion mobile phase was acetonitrile and 0.01% ammonia aqueous solution to detect estrogen. The results showed that the 15 kinds of sex hormone residues in shrimp meat samples purified by EMR solid phase extraction had a good linear relationship in the concentration range of 1~50 μg/kg, and the correlation coefficients (r) were all greater than 0.99. The detection limits of the method were 0.0015~0.436 μg/kg, and the quantitative limits were 0.0051~1.453 μg/kg. The average recoveries were 85.31%~119.84%, and the relative standard deviations were 2.11%~9.86% (n=6). The method was rapid, simple, reproducible and sensitive, which was suitable for the detection of 15 kinds of sex hormone residues in shrimp meat.