25495-26-5Relevant articles and documents
Gas chromatography/chemical ionization triple quadrupole mass spectrometry analysis of anabolic steroids: Ionization and collision-induced dissociation behavior
Polet, Michael,Van Gansbeke, Wim,Van Eenoo, Peter,Deventer, Koen
, p. 511 - 522 (2016/02/09)
Rationale The detection of new anabolic steroid metabolites and new designer steroids is a challenging task in doping analysis. Switching from electron ionization gas chromatography triple quadrupole mass spectrometry (GC/EI-MS/MS) to chemical ionization (CI) has proven to be an efficient way to increase the sensitivity of GC/MS/MS analyses and facilitate the detection of anabolic steroids. CI also extends the possibilities of GC/MS/MS analyses as the molecular ion is retained in its protonated form due to the softer ionization. In EI it can be difficult to find previously unknown but expected metabolites due to the low abundance or absence of the molecular ion and the extensive (and to a large extent unpredictable) fragmentation. The main aim of this work was to study the CI and collision-induced dissociation (CID) behavior of a large number of anabolic androgenic steroids (AAS) as their trimethylsilyl derivatives in order to determine correlations between structures and CID fragmentation. Clarification of these correlations is needed for the elucidation of structures of unknown steroids and new metabolites. Methods The ionization and CID behavior of 65 AAS have been studied using GC/CI-MS/MS with ammonia as the reagent gas. Glucuronidated AAS reference standards were first hydrolyzed to obtain their free forms. Afterwards, all the standards were derivatized to their trimethylsilyl forms. Full scan and product ion scan analyses were used to examine the ionization and CID behavior. Results Full scan and product ion scan analyses revealed clear correlations between AAS structure and the obtained mass spectra. These correlations were confirmed by analysis of multiple hydroxylated, methylated, chlorinated and deuterated analogs. Conclusions AAS have been divided into three groups according to their ionization behavior and into seven groups according to their CID behavior. Correlations between fragmentation and structure were revealed and fragmentation pathways were postulated.
Metabolism of anabolic steroids in humans: Synthesis of 6β-hydroxy metabolites of 4-chloro-1,2-dehydro-17α-methyltestosterone, fluoxymesterone, and metandienone
Schaenzer, Willi
, p. 353 - 366 (2007/10/02)
Hydroxylation at position 6β of testosterone I (17β-hydroxyandrost-4- en-3-one) and the anabolic steroids 17α-methyltestosterone II (17β-hydroxy- 17α-methylandrost-4-en-3-one), metandienone III (17β-hydroxy-17α- methylandrosta-1,4-dien-3-one), 4-chloro-1,2-dehydro-17α-methyltestosterone IV (4-chloro-17β-hydroxy-17α-methylandrosta-1,4-dien-3-one), and fluoxymesterone V (9-fluoro-11β, 17β-dihydroxy-17a-methylandrost-4-en-3- one) was achieved via light-induced autooxidation of the corresponding trimethylsilyl 3,5-dienol ethers dissolved in isopropanol or ethanol. The reaction further yielded the 6α-hydroxy isomer in low amounts. The 6β- hydroxy isomers of I-V and the 6α-hydroxy isomers of I, III, and IV were isolated and characterized by 1H and 13C NMR, high-performance liquid chromatography, gas chromatography, and mass spectrometry. Human excretion studies with single administered doses of boldenone (17β-hydroxyandrosta- 1,4-dien-3-one), 4-chloro-1,2-dehydro-17α-methyltestosterone, fluoxymesterone, metandienone, 17α-methyltestosterone, and [16,16,17- 2H3]testosterone showed that 6β-hydroxylation is the major metabolic pathway in the metabolism of 4-chloro-1,2-dehydro-17α-methyltestosterone, fluoxymesterone, and metandienone, whereas for boldenone, 17α- methyltestosterone, and testosterone, 6β hydroxylation is negligable.
