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Interest of molecularly imprinted polymers in the fight against doping. Extraction of tamoxifen and its main metabolite from urine followed by high-performance liquid chromatography with UV detection.
J Chromatogr A. 2008 Jul 04; 1196-1197:81-8.JC

Abstract

A molecular imprinted polymer (MIP) has been synthesized in order to specifically extract tamoxifen, a nonsteroidal antiestrogen, and its metabolites from urine by solid-phase extraction (SPE) before HPLC-UV analysis. Clomiphene, a chlorinated tamoxifen analogue, was selected as template for MIP synthesis. Polymerisation was achieved by thermal polymerisation of methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate (EDMA) as cross-linking agent and acetonitrile as porogen. The efficient elimination of the urinary matrix has been obtained by MIP-SPE but the elution recovery of tamoxifen was initially too low (approximately 14%). This problem has been overcome following two ways. At first, a preliminary HLB-SPE of the urine has enabled to discard endogenous salts and to percolate an organic sample through the MIP cartridge. Extraction recoveries are equal to 56 and 74% for tamoxifen and 4-hydroxytamoxifen, respectively. Then, a second MIP has been prepared with styrene and MAA as functional co-monomers. Strong pi-pi interactions occurring between phenyl groups of styrene and tamoxifen promote rebinding of the analyte by the specific sites. The enhanced hydrophobic character of the imprinted polymer has enabled the direct percolation of urine through MIP-SPE and the easy elimination of endogenous salts from urine with only one aqueous washing step. HPLC-UV analysis has confirmed high extraction recoveries (85%) for tamoxifen and its metabolite with an enrichment factor of 8. This analytical protocol can selectively detect the presence of tamoxifen metabolites in urines and be useful as a proof of doping in competitive sports.

Authors+Show Affiliations

Institut de Chimie Organique et Analytique, CNRS FR 2708 UMR 6005, Université d'Orléans, 45067 Orléans, France. berengere.claude@univ-orleans.frNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

18538333

Citation

Claude, Bérengère, et al. "Interest of Molecularly Imprinted Polymers in the Fight Against Doping. Extraction of Tamoxifen and Its Main Metabolite From Urine Followed By High-performance Liquid Chromatography With UV Detection." Journal of Chromatography. A, vol. 1196-1197, 2008, pp. 81-8.
Claude B, Morin P, Bayoudh S, et al. Interest of molecularly imprinted polymers in the fight against doping. Extraction of tamoxifen and its main metabolite from urine followed by high-performance liquid chromatography with UV detection. J Chromatogr A. 2008;1196-1197:81-8.
Claude, B., Morin, P., Bayoudh, S., & de Ceaurriz, J. (2008). Interest of molecularly imprinted polymers in the fight against doping. Extraction of tamoxifen and its main metabolite from urine followed by high-performance liquid chromatography with UV detection. Journal of Chromatography. A, 1196-1197, 81-8. https://doi.org/10.1016/j.chroma.2008.05.022
Claude B, et al. Interest of Molecularly Imprinted Polymers in the Fight Against Doping. Extraction of Tamoxifen and Its Main Metabolite From Urine Followed By High-performance Liquid Chromatography With UV Detection. J Chromatogr A. 2008 Jul 4;1196-1197:81-8. PubMed PMID: 18538333.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Interest of molecularly imprinted polymers in the fight against doping. Extraction of tamoxifen and its main metabolite from urine followed by high-performance liquid chromatography with UV detection. AU - Claude,Bérengère, AU - Morin,Philippe, AU - Bayoudh,Sami, AU - de Ceaurriz,Jacques, Y1 - 2008/05/21/ PY - 2008/02/04/received PY - 2008/05/15/revised PY - 2008/05/16/accepted PY - 2008/6/10/pubmed PY - 2008/9/25/medline PY - 2008/6/10/entrez SP - 81 EP - 8 JF - Journal of chromatography. A JO - J Chromatogr A VL - 1196-1197 N2 - A molecular imprinted polymer (MIP) has been synthesized in order to specifically extract tamoxifen, a nonsteroidal antiestrogen, and its metabolites from urine by solid-phase extraction (SPE) before HPLC-UV analysis. Clomiphene, a chlorinated tamoxifen analogue, was selected as template for MIP synthesis. Polymerisation was achieved by thermal polymerisation of methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate (EDMA) as cross-linking agent and acetonitrile as porogen. The efficient elimination of the urinary matrix has been obtained by MIP-SPE but the elution recovery of tamoxifen was initially too low (approximately 14%). This problem has been overcome following two ways. At first, a preliminary HLB-SPE of the urine has enabled to discard endogenous salts and to percolate an organic sample through the MIP cartridge. Extraction recoveries are equal to 56 and 74% for tamoxifen and 4-hydroxytamoxifen, respectively. Then, a second MIP has been prepared with styrene and MAA as functional co-monomers. Strong pi-pi interactions occurring between phenyl groups of styrene and tamoxifen promote rebinding of the analyte by the specific sites. The enhanced hydrophobic character of the imprinted polymer has enabled the direct percolation of urine through MIP-SPE and the easy elimination of endogenous salts from urine with only one aqueous washing step. HPLC-UV analysis has confirmed high extraction recoveries (85%) for tamoxifen and its metabolite with an enrichment factor of 8. This analytical protocol can selectively detect the presence of tamoxifen metabolites in urines and be useful as a proof of doping in competitive sports. SN - 0021-9673 UR - https://www.unboundmedicine.com/medline/citation/18538333/Interest_of_molecularly_imprinted_polymers_in_the_fight_against_doping__Extraction_of_tamoxifen_and_its_main_metabolite_from_urine_followed_by_high_performance_liquid_chromatography_with_UV_detection_ L2 - https://linkinghub.elsevier.com/retrieve/pii/S0021-9673(08)00874-1 DB - PRIME DP - Unbound Medicine ER -