title: New potential biomarkers for mesterolone misuse in human urine by liquid chromatography quadrupole time-of-flight mass spectrometry.
abstract: In this paper, mesterolone metabolic profiles were investigated carefully. Mesterolone was administered to one healthy male volunteer. Urinary extracts were analyzed by liquid chromatography quadruple time-of-flight mass spectrometry (LC-QTOFMS) for the first time. Liquid-liquid extraction was applied to processing urine samples, and dilute-shoot analyses of intact metabolites were also presented. In LC-QTOFMS analysis, chromatographic peaks for potential metabolites were hunt down by using the theoretical [M-H](-) as target ions in full scan experiment, and their actual deprotonated ions were analyzed in targeted MS/MS mode. Ten metabolites including seven new sulfate and three glucuronide conjugates were found for mesterolone. Because of no useful fragment ion for structural elucidation, gas chromatography-mass spectrometry instrumentation was employed to obtain structural details of the trimethylsilylated phase I metabolite released after solvolysis. Thus, their potential structures were proposed particularly by a combined MS approach. All the metabolites were also evaluated in terms of how long they could be detected, and S1 (1α-methyl-5α-androst-3-one-17β-sulfate) together with S2 (1α-methyl-5α-androst-17-one-3β-sulfate) was detected up to 9 days after oral administration, which could be the new potential biomarkers for mesterolone misuse.
authors.affiliation: National Anti-doping Laboratory, China Anti-doping Agency, 1st Anding Road, ChaoYang District, Beijing, 100029, China.
authors.forename: Jianghai
authors.initials: J
authors.lastname: Lu
authors.forename: María
authors.initials: M
authors.lastname: Fernández-Álvarez
authors.forename: Sheng
authors.initials: S
authors.lastname: Yang
authors.forename: Genye
authors.initials: G
authors.lastname: He
authors.forename: Youxuan
authors.initials: Y
authors.lastname: Xu
authors.forename: Rodigo
authors.initials: R
authors.lastname: Aguilera
mesh_terms: D000284:Administration, Oral; D000328:Adult; D045930:Anabolic Agents / Q000652:urine; D015415:Biomarkers / Q000652:urine*; D002853:Chromatography, Liquid / Q000379:methods*; D004300:Doping in Sports; D008401:Gas Chromatography-Mass Spectrometry; D020719:Glucuronides / Q000737:chemistry / Q000378:metabolism / Q000652:urine; D006801:Humans; D059625:Liquid-Liquid Extraction; D008297:Male; D013058:Mass Spectrometry / Q000295:instrumentation / Q000379:methods*; D008655:Mesterolone / Q000008:administration & dosage / Q000031:analogs & derivatives / Q000378:metabolism* / Q000652:urine*; D053719:Tandem Mass Spectrometry / Q000379:methods
chemical_list: C000601353:1-methylandrost-17-one-3-sulfate; C000601352:1-methylandrost-3-one-17-sulfate; D045930:Anabolic Agents; D015415:Biomarkers; D020719:Glucuronides; D008655:Mesterolone
keywords: doping control; human urine; liquid chromatography quadruple time-of-flight mass spectrometry; mesterolone; new metabolites