气相色谱-质谱联用法同时测定牛奶中的6种天然雌激素  

Simultaneous Determination of Six Natural Estrogens in Milk by Gas Chromatography-Mass Spectrometry

作　　者：孔德明 陈超 周启动 刘则华 郭鹏然 KONG De-ming;CHEN Chao;ZHOU Qi-dong;LIU Ze-hua;GUO Peng-ran(Guangdong Provincial Key Laboratory of Chemical Measurement and Emergency Test Technology,Institute of Analysis,Guangdong Academy of Sciences(China National Analytical Center,Guangzhou),Guangzhou 510070,China;School of Environment and Energy,South China University of Technology,Guangzhou 510006,China)

机构地区：[1]广东省科学院测试分析研究所(中国广州分析测试中心),广东省化学测量与应急检测重点实验室,广东广州510070 [2]华南理工大学环境与能源学院,广东广州510006

出　　处：《分析测试学报》2023年第2期216-220,共5页Journal of Instrumental Analysis

基　　金：广东省科学院发展专项资金项目(2020GDASYL-20200103047)。

摘　　要：天然雌激素是一类内源性激素,但其外源性摄入可能对人体健康造成危害。牛奶是人体外源性天然雌激素的重要来源之一,对牛奶中天然雌激素的准确分析是评价人体外源摄入的重要前提。该研究建立了一种气相色谱-质谱联用(GC-MS)同时测定牛奶中雌酮(E1)、17α-雌二醇(17α-E2)、17β-雌二醇(E2)、雌三醇(E3)、16α-羟基雌酮(16αOHE1)和16keto雌二醇(16ketoE2)6种天然雌激素的分析方法。选择不同类型牛奶样品,依次通过液液萃取、固相萃取富集净化,再利用BSTFA+1%TMCS进行衍生化,乙酸乙酯定容后采用GC-MS进行测定。结果显示,6种雌激素在5~100μg/L范围内线性关系良好,相关系数(r^(2))大于0.995;检出限(LOD)和定量下限(LOQ)分别为0.17~0.51μg/L和0.56~1.68μg/L;平均加标回收率为83.1%~119%,相对标准偏差(RSD)为2.1%~15%,该方法具有较好的准确性及稳定性。利用所建方法对实际牛奶样品中的天然雌激素进行检测,除常见的天然雌激素E1、E2、17α-E2之外,样品中还检测出16αOHE1和16ketoE2。方法适用于牛奶中天然雌激素的检测和质量控制。Natural estrogens are a class of endogenous hormones,but their exogenous intake may still be harmful to human health.Milk is one of the significant sources of exogenous natural estrogens in humans.Therefore,accurate analysis of natural estrogen in milk is an important prerequisite for evaluating its exogenous intake. In this paper, a gas chromatography-mass spectrometric(GCMS) method was developed for the simultaneous determination of six natural estrogens in milk,including estrone(E1),17α-estradiol(17α-E2),17β-estradiol(E2),estriol(E3),16α-hydroxyl estrone(16αOHE1) and 16ketoestradiol(16ketoE2).Milk samples were extracted with acetonitrile,enriched and purified with a OASIS HLB Cartridge in turn,then derivatized with BSTFA+1% TMCS.The results showed that six estrogens had good linear relationships in the concentration range of 5-100 μg/L,with correlation coefficients(r~2) larger than 0. 995.The limits of detection(LODs) and limits of quantitation(LOQs) were in the range of 0. 17-0. 51 μg/L and 0. 56-1. 68 μg/L,respectively.The average recoveries ranged from 83. 1% to 119%,with relative standard deviations(RSDs,n = 9) of 2. 1%-15%.The method was applied to the detection of natural estrogens in actual milk samples, and all the estrogens compounds were detected in except E3, indicating that 16αOHE1and 16ketoE2 should not be ignored.With good accuracy and precision,this method is suitable for the detection of natural estrogens in milk.

关 键 词：牛奶 天然雌激素 气相色谱-质谱法(GC-MS) 液液萃取 固相萃取 

分 类 号：O657.63[理学—分析化学] O629.8[理学—化学]