整体柱在线固相微萃取-高效液相色谱法分析爽肤水中痕量雌激素

以甲基丙烯酸缩水甘油酯(GMA)为功能单体、乙二醇二甲基丙烯酸酯(EDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂、甲醇及正己烷(14∶5,v/v)为二元致孔剂,通过原位聚合反应制备了聚甲基丙烯酸缩水甘油酯(Poly(GMA-co-EDMA))毛细管整体柱。研究表明,制备的Poly(GMA-co-EDMA)整体柱具有良好的通透性和较低的柱压(1.5×106Pa,冲洗流速0.5 mL/min)。该整体柱对雌二醇、炔雌醇、雌酮和己烯雌酚的富集倍数分别为86、116、77和86。构建了整体柱在线微萃取接口装置,建立了整体柱在线固相微萃取-高效液相色谱(HPLC)测定爽肤水中痕量雌二醇、炔雌醇、雌酮和己烯雌酚的分析方法。该分析方法的检出限(S/N=3)为0.05~0.20μg/L。将方法应用于爽肤水中雌激素的检测,加标回收率为69.3%~111.3%,RSD5.0%。所建立的方法简单、快速、灵敏、准确,可满足爽肤水中痕量雌激素的分析。

Analysis of trace estrogens in toners by monolithic column online solid phase microextraction coupled with high performance liquid chromatography

A Poly(glycidyl methacrylate-co-ethyleneglycol dimethacrylate) (Poly(GMA-co-EDMA)) monolithic column was prepared in a capillary by in-situ polymerization. Glycidyl methacrylate (GMA) was chosen to be the monomer and ethyleneglycol dimethacrylate (EDMA) was utilized as crosslinking agent. The binary porogenic agents of methanol and n-hexane can develop the permeability of monolithic column and they were suitable to construct the online analysis apparatus. A series of experiments were carried out, and they demonstrated the monolithic column had good permeability with low column pressure (1.5×10⁶ Pa at the washing flow rate of 0.5 mL/min). The enrichment factors of the prepared monolithic column for estradiol, ethynyl estradiol, estrone and diethylstilbestrol were 86, 116, 77 and 86, respectively. It was proved that the monolithic column was suitable for the online microextraction system by using the interface unit. A method was established for the analysis of trace estradiol, ethynyl estradiol, estrone and diethylstilbestrol in toners by monolithic column online solid phase microextraction coupled with high performance liquid chromatography. The limits of detection (S/N=3) were 0.05-0.20 μg/L. The recoveries in toner samples varied from 69.3% to 111.3%, and relative standard deviations were less than 5.0%. The method is efficient, sensitive, accurate, reliable and applicable to analyze trace estrogens in toners.