Abstract
Protein removal process is always time-consuming for the analysis of milk samples. In this work, hollow fiber membrane-coated functionalized polymeric ionic liquid (HF-PIL) capsules were synthesized and used as solid-phase microextraction (SPME) sorbent for direct analysis of estrogens in milk samples. The functionalized PIL monolith sorbent was obtained by copolymerization between 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate IL monomer and 1,6-di(3-vinylimidazolium) hexane bishexafluorophosphate IL-crosslinking agent. A group of four capsules were installed as SPME device, to determine four kinds of estrogens (estrone, diethylstilbestrol, hexestrol, and 17α-ethynylestradiol) in milk samples, coupled to high performance liquid chromatography. Extraction and desorption conditions were optimized to get satisfactory extraction efficiency. Good linearity was obtained in the range of 5–200 μg L−1. The limits of detection were 1 μg L−1 for diethylstilbestrol and 2 μg L−1 for 17α-ethynylestradiol, estrone, and hexestrol. The present method was applied to analyze the model analytes in different milk samples. Relative recoveries were in the range of 85.5–112 %. The HF-PIL SPME capsules showed satisfactory extraction efficiency and high resistance to sample matrix interference.
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Direct analysis of estrogens in milk samples by hollow fiber membrane-coated functionalized polymeric ionic liquids SPME capsules.
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References
Flores-Flores ME, Lizarraga E, de Cerain AL, González-Peñas E. Presence of mycotoxins in animal milk: a review. Food Control. 2015;53:163–76.
Thompson TS, Noot DK, Kendall JD. Determination of ionophores in raw bovine milk using LC-MS/MS: application to residue surveillance. Food Chem. 2011;127:321–6.
Castagnetta L, Granata OM, Cocciadiferro L, Saetta A, Polito L, Bronte G, et al. Sex steroids, carcinogenesis, and cancer progression. Ann NY Acad Sci. 2004;1028:233–46.
Socas-Rodríguez B, Asensio-Ramos M, Hernández-Borges J, Herrera AV, Rodríguez-Delgado MÁ. Chromatographic analysis of natural and synthetic estrogens in milk and dairy products. Trends Anal Chem. 2013;44:58–77.
Zheng H-B, Mo J-Z, Zhang Y, Gao Q, Ding J, Yu Q-W, et al. Facile synthesis of magnetic molecularly imprinted polymers and its application in magnetic solid phase extraction for fluoroquinolones in milk samples. J Chromatogr A. 2014;1329:17–23.
Synaridou M-E S, Sakkas VA, Stalikas CD, Albanis TA. Evaluation of magnetic nanoparticles to serve as solid-phase extraction sorbents for the determination of endocrine disruptors in milk samples by gas chromatography mass spectrometry. J Chromatogr A. 2014;1348:71–9.
Moreno-Gronzález D, Lara FJ, Gámiz-Gracia L, García-Campaña AM. Molecularly imprinted polymer as in-line concentration in capillary electrophoresis coupled with mass spectrometry for the determination of quinolones in bovine milk samples. J Chromatogr A. 2014;1360:1–8.
Zhang Y, Lin S, Jiang P, Zhu X, Ling J, Zhang W, et al. Determination of melamine and cyromazine in milk by high performance liquid chromatography coupled with online solid-phase extraction using a novel cation-exchange restricted access material synthesized by surface initiated atom transfer radical polymerization. J Chromatogr A. 2014;1337:17–21.
Hagestam IH, Pinkerton TC. Internal surface reversed-phase silica supports for liquid chromatography. Anal Chem. 1985;57:1757–63.
Chiap P, Rbeida O, Christiaens B, Hubert P, Lubda D, Boos K-S, et al. Use of a novel cation-exchange restricted-access material for automated sample clean-up prior to the determination of basic drugs in plasma by liquid chromatography. J Chromatogr A. 2002;975:145–55.
Basheer C, Lee HK. Hollow fiber membrane-protected solid-phase microextraction of trazine herbicides in bovine milk and sewage sludge samples. J Chromatogr A. 2004;1047:189–94.
Pedersen-Bjergaard S, Rasmussen KE. Liquid-liquid-liquid microextraction for sample preparation of biological fluids prior to capillary electrophoresis. Anal Chem. 1999;71:2650–6.
Carasek E, Merib J. Membrane-based microextraction techniques in analytical chemistry: a review. Anal Chim Acta. 2015;880:8–25.
Chen B, Huang Y, He M, Hu B. Hollow fiber liquid-liquid-liquid microextraction combined with high performance liquid chromatography-ultraviolet detection for the determination of various environmental estrogens in environmental and biological samples. J Chromtogr A. 2013;1305:17–26.
Xu X, Liang F, Shi J, Zhao X, Liu Z, Wu L, et al. Determination of hormones in milk by hollow fiber-based stirring extraction bar liquid-liquid microextraction gas chromatography mass spectrometry. J Chromatogr A. 2013;790:39–46.
Peng J-F, Liu J-F, Hu X-L, Jiang G-B. Direct determination of chlorophenols in environmental water samples by hollow fiber supported ionic liquid membrane extraction coupled with high-performance liquid chromatography. J Chromatogr A. 2007;1139:165–70.
Ge D, Lee HK. Ultra-hydrophobic ionic liquid 1-hexyl-3-emthylimidazolium tris(pentafluoroethyl)trifluorophosphate supported hollow-fiber membrane liquid-liquid-liquid microextraction of chlorophenols. Talanta. 2015;132:132–6.
Meng Y, Anderson J. Tuning the selectivity of polymeric ionic liquid sorbent coating for the extraction of polymeric aromatic hydrocarbons using solid-phase microextraction. J Chromatogr A. 2010;1217:6143–52.
Feng J, Sun M, Li J, Liu X, Jiang S. A novel aromatically functional polymeric ionic liquid as sorbent material for solid-phase microextraction. J Chromatogr A. 2012;1227:54–9.
Feng J, Sun M, Bu Y, Luo C. Development of a functionalized polymeric ionic liquid monolith for solid-phase microextraction of polar endocrine disrupting chemicals in aqueous samples coupled to high performance liquid chromatography. Anal Bioanal Chem. 2015;407:7025–35.
Xie X, Pan X, Han S, Wang S. Development and characterization of magnetic molecularly imprinted polymers for the selective enrichment of endocrine disrupting chemicals in water and milk samples. Anal Bioanal Chem. 2015;407:1735–44.
Yang Y, Chen J, Shi Y-P. Determination of diethylstilbestrol in milk using carbon nanotube-reinforced hollow fiber solid-phase microextraction combined with high-performance liquid chromatography. Talanta. 2012;97:222–8.
Liu M, Li M, Qiu B, Chen X, Chen G. Synthesis and application of diethylstilbestrol-based molecularly imprinted polymer-coated hollow fiber tube. Anal Chim Acta. 2010;663:33–8.
Zhao C, Guan X, Liu X, Zhang H. Synthesis of molecularly imprinted polymer using attapulgite as matrix by ultrasonic irradiation for simultaneous on-line solid phase extraction and high performance liquid chromatography determination of four estrogens. J Chromatogr A. 2012;1229:72–8.
Acknowledgments
This work was supported by the National Natural Science Foundation of China (NSFC, Nos. 21405061 and 21205048), the Shandong Provincial Natural Science Foundation of China (No. ZR2014BQ019), and the Doctoral Foundation of University of Jinan (No. XBS1410).
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Feng, J., Sun, M., Bu, Y. et al. Hollow fiber membrane-coated functionalized polymeric ionic liquid capsules for direct analysis of estrogens in milk samples. Anal Bioanal Chem 408, 1679–1685 (2016). https://doi.org/10.1007/s00216-015-9279-9
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DOI: https://doi.org/10.1007/s00216-015-9279-9