Gas Phase Analytical Methods for the Study of Steroids

Mass spectrometry in sports drug testing: Structure characterization and analytical assays

“…The fragmentation to m/z 246 was postulated to be initiated by the removal of an pelectron from the a,b-unsaturated system followed by the elimination of ketene (À42 u) forming a 4-member ring structure (Scheme 2b), and the common losses of a water molecule or a methyl radical give rise to m/z 270 and 272, respectively. While the eliminations of 15, 18, or 42 have also been observed with other a,b-unsaturated nuclei (e.g., 3-keto-1-ene steroids), the fragment ion at m/z 124 has demonstrated considerable specificity for a testosterone-related steroid structure (Horning, Brooks, & Vanden Heuvel, 1968). The location of a double bond between C-1 and C-2 instead of C-4 and C-5 causes the formation of a fragment ion at m/z 122 (Table 1, 6), the formation of which is in accordance to the mechanism described for 3-keto-4-ene structures but includes the migration of the C-5-positioned hydrogen Djerassi, 1964).…”

“…Although of minor intensity, the fragment ion at m/z 129 is a valuable indicator for a derivatized 3-or 17-hydroxyl function of steroids. The origin of steroidal fragments at m/z 129 has been investigated in detail by analyses of stably deuterated or structurally closely related compounds (Diekman & Djerassi, 1967;Horning, Brooks, & Vanden Heuvel, 1968;Brooks et al, 1973;Masse, Laliberte, & Tremblay, 1985;Rendic, Nolteernsting, & Schänzer, 1999), and the proposed mechanisms of ion formations are shown in Scheme 3a.…”

Clinical steroid mass spectrometry: A 45-year history culminating in HPLC–MS/MS becoming an essential tool for patient diagnosis

“…The following sections describe early develop-0960-0760/$ -see front matter © 2010 Elsevier Ltd. All rights reserved. doi: 10.1016/j.jsbmb.2010.02.017 Table 1 The genesis of steroid mass spectrometry.…”

A guide to understanding the steroid pathway: New insights and diagnostic implications

“…Since the development of the early radioimmunoassays (RIA) for serum steroids [1] and gas chromatography (GC) metabolomic methods for urine steroids [2][3][4][5] in the 1960's, there have been significant advances in our understanding and quantification of these remarkable hormones. Recent refinements in mass spectrometry and molecular techniques have resulted in a paradigm shift in steroid analysis.…”