衍生瓜环固相微萃取搅拌棒-高效液相色谱测定食品中残留雌激素

Determination of Estrogens in Foods by Derived CucurbiturilCoated Stir Bar Sorptive Extraction Combined with High-Performance Liquid Chromatography

建立了基于单羟基取代七元瓜环的固相微萃取搅拌棒(SBSE)-液体解析(LD)-高效液相色谱(HPLC)-紫外吸收检测器(UV)同时测定动物源性食品(猪肉,鸡肉)中残留的3种雌激素(双酚A(BPA)、雌二醇(E2)和己烯雌酚(DES))的测定方法。以单羟基七元瓜环(Q7-OH)和羟基聚二甲基硅氧烷(PDMS-OH)为固定相,采用溶胶-凝胶法制备了PDMS/Q7-OH涂层的固相微萃取小棒。萃取小棒表面粗糙、多孔、制备重复精度好(RSD≤8.4%)、使用寿命长。萃取机理的考察实验结果表明,小棒萃取效率的提高源于七元瓜环对分析物具有较好的分子识别能力。在优化的实验条件下,建立的PDMS/Q7-OH SBSE-LD-HPLC-UV分析方法对3种雌激素的检出限为0.05～0.56μg/L,富集倍数19～25倍,线性范围在0.2～5000μg/L之间,RSD为3.9%～7.5%(n=5,C=100μg/L),3个浓度水平的平均回收率(n=3)在72.7%～109.2%范围内。本方法简单、灵敏、选择性好,可用于动物源性食品(猪肉,鸡肉)中残留雌激素的检测。

A method of stir bar sorptive extraction(SBSE)based on monohydroxyl cucurbit7 uril(Q7-OH)-liquid desorption(LD)-high performance liquid chromatography(HPLC)-ultraviolet detection was developed for measurement of three residual estrogens(bisphenol A,estradiol and diethylstillbestrol)from animal-derived foods(pork and chicken samples).The hydroxyl polydimethylsiloxane(PDMS-OH)/Q7-OH-coated stir bar was conducted by the sol-gel technique with the synthesized Q7-OH as a selective stationary phase.The innovative SBSE exhibited a rough and porous surface structure,a good preparation reproducibility(RSD≤8.4%)and a long lifespan.Extraction mechanism indicated that the increase of extraction efficiency was attributed to the excellent molecular recognition of Q7 towards analytes.Under the optimal experimental conditions,the limits of detection of the developed PDMS/Q7-OH SBSE-LD-HPLC-UV method were 0.05-0.56μg/L for the target estrogens with enrichment factors of 19-25 folds,the dynamic linear range was 0.2-5000μg/L,and the RSDs were in the range of 3.9%-7.5%(n=5,C=100μg/L).The mean recoveries(n=3)at three different concentration levels were 72.7%-109.2%.The developed method was simple,sensitive,and selective,and was successfully applied to the analysis of estrogens in animal-derived foods(pork and chicken samples).