Improved Steroids Detection and Evidence for Their Regiospecific Decompositions Using Anion Attachment Mass Spectrometry

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• 作者：Quentin Dumont ; Mariana Bárcenas ; Héloïse Dossmann ; Isabelle Bailloux ; Corinne Buisson ; Nathalie Mechin ; Adeline Molina ; Françoise Lasne ; Nalaka S. Rannulu ; Richard B. Cole
• 刊名：Analytical Chemistry
• 出版年：2016
• 出版时间：April 5, 2016
• 年：2016
• 卷：88
• 期：7
• 页码：3585-3591
• 全文大小：359K
• ISSN：1520-6882

文摘

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.