QuEChERS法结合UHPLC-MS/MS同时测定化妆品中34种性激素

Simultaneous Determination of 34 Sexual Hormones in Cosmetics by QuEChERS Method and UHPLC-MS/MS

关键词:  QuEChERS  性激素类  高效液相色谱-串联质谱法  化妆品

Key words:  QuEChERS  sexual hormones  UHPLC-MS/MS  cosmetics

摘要:

目的 建立同时测定3种不同基质类型（水剂、乳液类和膏霜类）化妆品中34种性激素类禁用化合物的超高效液相色谱-串联质谱（UHPLC-MS/MS）法。方法 样品经溶剂超声提取，再采用不同的盐析剂和净化剂QuEChERS方法净化后上机检测。采用Agilent ZORBAX SB C₁₈（2.1 mm×50 mm，1.8 μm）色谱柱，以乙腈-水作为流动相梯度洗脱，电喷雾离子源多反应监测方式检测，基质匹配标准曲线外标法定量。结果 34种性激素类化合物在一定浓度范围内具有良好的线性关系，相关系数（r²）>0.99，方法的检出限与定量限分别为0.005~0.29 mg·kg^-1和0.02~0.95 mg·kg^-1。3个不同浓度添加水平下，水剂、乳液类和膏霜类样品回收率分别为88.3%~111.4%，89.4%~114.6%和86.9%~114.2%，RSD均<10%。应用该方法对样品进行了检验，在2批育发类化妆品中检出了黄体酮。结论 该方法准确、高效、前处理简单，适用于化妆品中34种性激素类化合物的测定。

Abstract:

OBJECTIVE To establish a high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the simultaneous determination of 34 kinds of prohibited sexual hormones in 3 different matrixes of cosmetics(water aqua, lotion and cream). METHODS Samples were ultrasonically extracted by solvent, and then purified by QuEChERS method with different kinds of salting out agent and purifying agent. The separation was performed on an Agilent ZORBAX SB C₁₈ column(2.1 mm×50 mm, 1.8 μm) with gradient elution using acetonitrile and water as the mobile phase. The determination was performed by MS/MS in multiple reaction monitoring(MRM) mode. Matrix matching calibration method was used for the quantification. RESULTS The results demonstrated that all 34 kinds of sexual hormones could be well separated. There were good linear relationships for the 34 compounds in the certain concentration ranges with their correlation coefficients (r²) larger than 0.99. The limits of detection and limits of quantification were in the range of 0.005-0.29 mg·kg^-1 and 0.02-0.95 mg·kg^-1, respectively. At 3 different concentrations, the recoveries of water aqua, lotion and cream samples were 88.3%-111.4%, 89.4%-114.6% and 86.9%-114.2%, respectively. And RSD were less than 10.0%. The method was used to test the samples, and progesterone was detected in two hair growth cosmetics. CONCLUSION The present method is accurate, efficient and easy pretreatment, and can be applied in the determination of the 34 sexual hormones in cosmetic products.