超高效液相色谱-大气压化学电离-三重四极杆质谱法同时测定保健食品中14种性激素类药物

Simultaneous determination of 14 sexual hormones in health care products by ultra performance liquid chromatography-atmospheric pressure chemical ionization-triple quadrupole mass spectrometry

建立了超高效液相色谱-大气压化学电离-三重四极杆质谱(UPLC-APCI-MS/MS)测定保健食品中14种性激素类药物的方法。样品用乙腈提取2次,再用HLB固相萃取柱净化处理。采用Hypersil Gold C18色谱柱(100 mm×2.1 mm, 1.9 μm)分离,以乙腈-10 mmol/L 乙酸铵溶液为流动相进行梯度洗脱,采用APCI-三重四极杆质谱检测,外标法定量。结果表明,14种性激素类药物在各自范围内线性关系良好,相关系数( r )≥0.996,检出限为 0.099 0 ~2.09 μg/kg ,定量限为0.495~5.23 μg/kg;在低、中、高3个水平下的平均加标回收率为65.8%~118.8%,精密度为0.6%~8.7%( n =6)。该方法前处理简单,灵敏度高,回收率良好,适用于保健食品中性激素类非法添加物的定量测定。

A comprehensive analytical method was developed for the simultaneous determination of 14 sexual hormones in health care products by ultra performance liquid chromatography-atmospheric pressure chemical ionization-triple quadrupole mass spectrometry (UPLC-APCI-MS/MS). The samples were extracted twice with acetonitrile and the extracts were purified using hydrophilic-lipophilic balance (HLB) cartridges. Chromatographic separation was achieved on a Hypersil Gold C18 column (100 mm×2.1 mm, 1.9 μm) by gradient elution with acetonitrile and 10 mmol/L ammonium acetate aqueous solution as the mobile phases. Compounds were detected by APCI-MS/MS with external standard calibration curve method. All the 14 sexual hormones showed a good linear trend in their respective concentration ranges and the correlation coefficients ( r ) were no less than 0.996. The limits of detection (LODs) ranged from 0.099 0 μg/kg to 2.09 μg/kg . The limits of quantification (LOQs) were in the range of 0.495-5.23 μg/kg . The average recoveries of the 14 sexual hormones in the health care product samples ranged from 65.8% to 118.8% at the three spiked levels. The precisions ( n =6) ranged from 0.6% to 8.7%( n =6). The method is simple, sensitive, accurate and precise, and is suitable for the determination of the illegal added sexual hormones in the health care products.