title: Improved Steroids Detection and Evidence for Their Regiospecific Decompositions Using Anion Attachment Mass Spectrometry.
abstract: Nonpolar anabolic steroids are doping agents that typically do not provide strong signals by electrospray ionization-mass spectrometry (ESI-MS) owing especially to the low polarity of the functional groups present. We have investigated the addition of anions, in ammonium salt form, to anabolic steroid samples as ionization enhancers and have confirmed that lower instrumental limits of detection (as low as 10 ng/mL for fluoxymesterone-M) are obtained by fluoride anion attachment mass spectrometry, as compared to ESI(+)/(-) or atmospheric pressure photoionization (APPI)(+). Moreover, collision-induced decomposition (CID) spectra of precursor fluoride adducts of the bifunctional steroid "reduced pregnenolone" (containing two hydroxyl groups) and its d4-analogue provide evidence of regiospecific decompositions after attachment of fluoride anion to a specific hydroxyl group of the steroid. This type of charting of specific CID reaction pathways can offer value to selected reaction monitoring experiments (SRM) as it may result in a gain in selectivity in detection as well as in improvements in quantification.
authors.affiliation: Sorbonne Universités , UPMC Univ Paris 06, CNRS, Institut Parisien de Chimie Moléculaire (IPCM), 4 Place Jussieu 75252 Paris Cedex 05, France.
authors.forename: Quentin
authors.initials: Q
authors.lastname: Dumont
authors.affiliation: Sorbonne Universités , UPMC Univ Paris 06, CNRS, Institut Parisien de Chimie Moléculaire (IPCM), 4 Place Jussieu 75252 Paris Cedex 05, France.
authors.forename: Mariana
authors.initials: M
authors.lastname: Bárcenas
authors.affiliation: Sorbonne Universités , UPMC Univ Paris 06, CNRS, Institut Parisien de Chimie Moléculaire (IPCM), 4 Place Jussieu 75252 Paris Cedex 05, France.
authors.forename: Héloïse
authors.initials: H
authors.lastname: Dossmann
authors.affiliation: Agence Française de Lutte Contre le Dopage , Département des Analyses, 143 Avenue Roger Salengro, 92290 Châtenay-Malabry, France.
authors.forename: Isabelle
authors.initials: I
authors.lastname: Bailloux
authors.affiliation: Agence Française de Lutte Contre le Dopage , Département des Analyses, 143 Avenue Roger Salengro, 92290 Châtenay-Malabry, France.
authors.forename: Corinne
authors.initials: C
authors.lastname: Buisson
authors.affiliation: Agence Française de Lutte Contre le Dopage , Département des Analyses, 143 Avenue Roger Salengro, 92290 Châtenay-Malabry, France.
authors.forename: Nathalie
authors.initials: N
authors.lastname: Mechin
authors.affiliation: Agence Française de Lutte Contre le Dopage , Département des Analyses, 143 Avenue Roger Salengro, 92290 Châtenay-Malabry, France.
authors.forename: Adeline
authors.initials: A
authors.lastname: Molina
authors.affiliation: Agence Française de Lutte Contre le Dopage , Département des Analyses, 143 Avenue Roger Salengro, 92290 Châtenay-Malabry, France.
authors.forename: Françoise
authors.initials: F
authors.lastname: Lasne
authors.affiliation: Department of Chemistry, University of New Orleans , 2000 Lakeshore Drive, New Orleans, Louisiana 70148, United States.
authors.forename: Nalaka S
authors.initials: NS
authors.lastname: Rannulu
authors.affiliation: Sorbonne Universités , UPMC Univ Paris 06, CNRS, Institut Parisien de Chimie Moléculaire (IPCM), 4 Place Jussieu 75252 Paris Cedex 05, France.|Department of Chemistry, University of New Orleans , 2000 Lakeshore Drive, New Orleans, Louisiana 70148, United States.
authors.forename: Richard B
authors.initials: RB
authors.lastname: Cole
mesh_terms: D064751:Ammonium Compounds / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D012492:Salts / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism; D013256:Steroids / Q000032:analysis* / Q000737:chemistry*
chemical_list: D064751:Ammonium Compounds; D000838:Anions; D012492:Salts; D013256:Steroids