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Identification of selenium species in urine by ion-pairing HPLC–ICP–MS using laboratory-synthesized standards

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Abstract

This study focused on the detection/identification of possible selenium metabolites in human urine. Organoselenium compounds not commercially unavailable were synthesized and characterized by electrospray mass spectrometry. Separation of selenomethionine, methylselenomethionine, trimethylselonium, selenoethionine, and selenoadenosylmethionine was achieved by ion-pairing HPLC with a mobile phase of 2 mmol L−1 hexanesulfonic acid, 0.4% acetic acid, 0.2% triethanolamine (pH 2.5), and 5% methanol. The column effluent was introduced on-line to inductively coupled plasma–mass spectrometry for selenium-specific detection (77Se and 78Se). For selenium speciation in urine, solid-phase extraction was carried out using C18 cartridges modified with hexanesulfonic acid. Selective retention of cationic species was observed from acidified urine (perchloric acid, pH 2.0). After elution with methanol, evaporation, and dissolution in the mobile phase, the sample was introduced to the HPLC–ICP–MS system and the chromatographic peaks were assigned by adding standards. The species identified in urine were selenomethionine, trimethylselonium ion, and selenoadenosylmethionine. The last species was detected for the first time and our results suggest that selenomethionine might enter the metabolic pathway of its sulfur analog in the activated methylation cycle.

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Acknowledgements

K. Wrobel and K. Wrobel sabbatical research leaves were supported by the University of Guanajuato, the University of Cincinnati, and by CONACyT, Mexico. The authors are grateful to the National Institute of Environmental Health Sciences for partial support of this work through grant number ES04908.

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Correspondence to Joseph A. Caruso.

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Kazimierz Wrobel and Katarzyna Wrobel are on the leave from the Institute of Scientific Research, University of Guanajuato, L. de Retana No. 5, 36000 Guanajuato, Gto., Mexico

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Wrobel, K., Wrobel, K., Kannamkumarath, S.S. et al. Identification of selenium species in urine by ion-pairing HPLC–ICP–MS using laboratory-synthesized standards. Anal Bioanal Chem 377, 670–674 (2003). https://doi.org/10.1007/s00216-003-2147-z

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  • DOI: https://doi.org/10.1007/s00216-003-2147-z

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