Solid-phase extraction using molecularly imprinted polymer for selective extraction of natural and synthetic estrogens from aqueous samples

• Published in: Journal of Chromatography A Vol. 1218; no. 30; pp. 4828 - 4833
• Main Authors: Lucci, Paolo, Núñez, Oscar, Galceran, M.T.
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 29.07.2011
• Subjects: Chromatography; Chromatography, High Pressure Liquid; correlation; detection limit; Dies; diethylstilbestrol; estradiol; Estradiol Congeners - analysis; Estradiol Congeners - chemistry; Estradiol Congeners - isolation & purification; estriol; Estrogens; Estrogens - analysis; Estrogens - chemistry; Estrogens - isolation & purification; estrone; Extraction; Imprinted polymers; Linear Models; Liquid chromatography; Mass Spectrometry; molecular imprinting; Molecular Imprinting - methods; Molecularly imprinted polymers; polymers; Recovery; Reproducibility of Results; rivers; Rivers - chemistry; Sensitivity and Specificity; solid phase extraction; Solid Phase Extraction - methods; Tap water; Ultrahigh pressure liquid chromatography; Water - chemistry; Water Pollutants, Chemical - analysis; Water Pollutants, Chemical - chemistry; Water Pollutants, Chemical - isolation & purification; Water samples; Ultrahigh pressure liquid chromatography; Molecularly imprinted polymers; Mass spectrometry; Estrogens; Water samples
• ISSN: 0021-9673; 1873-3778
• DOI: 10.1016/j.chroma.2011.02.007

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.