Department of Analytical Chemistry, University of Barcelona, Barcelona, Spain.
J Chromatogr A. 2011 Jul 29;1218(30):4828-33. doi: 10.1016/j.chroma.2011.02.007. Epub 2011 Feb 13.
A method is proposed for the clean-up and preconcentration of natural and synthetic estrogens from aqueous samples employing molecularly imprinted polymer (MIP) as selective sorbent for solid-phase extraction (SPE). The selectivity of the MIP was checked toward several selected natural and synthetic estrogens such as estrone (E1), 17β-estradiol (β-E2), 17α-estradiol (α-E2), estriol (E3), 17α-ethinylestradiol (EE2), dienestrol (DIES) and diethylstilbestrol (DES). Ultrahigh pressure liquid chromatography (UHPLC) coupled to a TSQ triple quadrupole mass spectrometry (QqQ) was used for analysis of target analytes. The chromatographic separation of the selected compounds was performed in less than 2 min under isocratic conditions. The method was applied to the analysis of estrogens in spiked river and tap water samples. High recoveries (>82%) for estrone, 17β-estradiol, 17α-estradiol, estriol and 17α-ethinylestradiol were obtained. Lower but still satisfactory recoveries (>48%) were achieved for dienestrol and diethylstilbestrol. The method was validated and found to be linear in the range 50-500 ng L(-1) with correlation coefficients (R(2)) greater than 0.995 and repeatability relative standard deviation (RSD) below 8% in all cases. For analysis of 100-mL sample, the method detection limits (LOD) ranged from 4.5 to 9.8 ng L(-1) and the limit of quantitation (LOQ) from 14.9 to 32.6 ng L(-1). To demonstrate the potential of the MIP obtained, a comparison with commercially available C(18) SPE was performed. Molecularly imprinted SPE showed higher recoveries than commercially available C(18) SPE for most of the compounds. These results showed the suitability of the MIP-SPE method for the selective extraction of a class of structurally related compounds such as natural and synthetic estrogens.
提出了一种从水样中用分子印迹聚合物（MIP）作为固相萃取（SPE）的选择性吸附剂来净化和预浓缩天然和合成雌激素的方法。通过 MIP 对几种选定的天然和合成雌激素（如雌酮（E1）、17β-雌二醇（β-E2）、17α-雌二醇（α-E2）、雌三醇（E3）、17α-乙炔基雌二醇（EE2）、双烯雌酚（DIES）和己烯雌酚（DES））的选择性进行了检查。超高效液相色谱（UHPLC）与 TSQ 三重四极杆质谱（QqQ）联用用于分析目标分析物。在等度条件下，选择的化合物在不到 2 分钟内实现了色谱分离。该方法应用于加标河水和自来水中雌激素的分析。雌酮、17β-雌二醇、17α-雌二醇、雌三醇和 17α-乙炔基雌二醇的回收率（>82%）较高。双烯雌酚和己烯雌酚的回收率较低（>48%），但仍令人满意。该方法经过验证，在 50-500 ng L(-1) 范围内呈线性，相关系数（R(2)）均大于 0.995，所有情况下重复性相对标准偏差（RSD）均低于 8%。对于 100-mL 样品的分析，方法检测限（LOD）范围为 4.5-9.8 ng L(-1)，定量限（LOQ）范围为 14.9-32.6 ng L(-1)。为了证明所获得的 MIP 的潜力，与市售的 C(18)SPE 进行了比较。对于大多数化合物，分子印迹 SPE 的回收率高于市售的 C(18)SPE。这些结果表明，MIP-SPE 方法适用于从水样中选择性提取一类结构相关的化合物，如天然和合成雌激素。
