title: Determination of selenium urinary metabolites by high temperature liquid chromatography-inductively coupled plasma mass spectrometry.
abstract: The coupling of high temperature liquid chromatography (HTLC) and inductively coupled plasma mass spectrometry (ICPMS) for the determination of selenium metabolites in urine samples is reported for the first time. In order to achieve "ICPMS-friendly" chromatographic conditions, the retention on a graphite stationary phase of the major selenium urinary metabolites using only plain water with 2% methanol as the mobile phase was investigated. Under the optimal conditions (T=80°C, Ql=1.2 mL min(-1)), methyl 2-acetamido-2-deoxy-1-seleno-β-d-galactopyranoside (selenosugar 1), methyl 2-acetamido-2-deoxy-1-seleno-β-d-glucosopyranoside (selenosugar 2) and trimethylselenonium ion were efficiently separated in less than 7 min, without any interferences due to other common selenium species (selenite, selenate, selenocystine and selenomethionine) or detectable effect of the urine matrix. The limits of detection were 0.3-0.5 ng Se mL(-1), and the precision of the analytical procedure was better than 3% (RSD%, n=5). The HTLC-ICPMS method was applied to the analysis of urine samples from two volunteers before and after ingestion of Brazil nuts or selenium supplements. The developed procedure proved to be adequate for the analytical task, providing results consistent with previous studies.
authors.affiliation: Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy.
authors.forename: A
authors.initials: A
authors.lastname: Terol
authors.affiliation: Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy.
authors.forename: F
authors.initials: F
authors.lastname: Ardini
authors.affiliation: Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy.
authors.forename: A
authors.initials: A
authors.lastname: Basso
authors.affiliation: Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy. Electronic address: grotti@unige.it.
authors.forename: M
authors.initials: M
authors.lastname: Grotti
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods; D003553:Cystine / Q000031:analogs & derivatives; D019587:Dietary Supplements; D006801:Humans; D013058:Mass Spectrometry / Q000379:methods; D016566:Organoselenium Compounds / Q000652:urine*; D064586:Selenic Acid / Q000652:urine; D020887:Selenious Acid / Q000652:urine; D018036:Selenium Compounds / Q000652:urine*; D012645:Selenomethionine / Q000652:urine
chemical_list: D016566:Organoselenium Compounds; D018036:Selenium Compounds; C009226:selenocystine; D003553:Cystine; D012645:Selenomethionine; D020887:Selenious Acid; D064586:Selenic Acid; C003717:trimethylselenonium
keywords: High temperature liquid chromatography; Hypercarb column; Selenium; Selenosugars; Speciation; Urine