Collision-induced dissociation pathways of anabolic steroids by electrospray ionization tandem mass spectrometry

Abstract

Anabolic steroids are structurally similar compounds, and their product-ion spectra obtained by tandem mass spectrometry under electrospray ionization conditions are quite difficult to interpret because of poly-ring structures and lack of a charge-retaining center in their chemical structures.In the present study, the fragmentation of nine anabolic steroids of interest to the racing industry was investigated by using triple quadrupole mass spectrometer, Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, and a linear ion trap instrument. With the aid of an expert system software (Mass Frontier version 3.0), accurate mass measurements, and multiple stage tandem mass spectrometric (MS n ) experiments, fragmentation pathways were elucidated for boldenone, methandrostenolone, tetrahydrogestrinone (THG), trenbolone, normethandrolone and mibolerone. Small differences in the chemical structures of the steroids, such as an additional double-bond or a methyl group, result in significantly different fragmentation pathways. The fragmentation pathways proposed in this paper allow interpretation of major product ions of other anabolic steroids reported by other researchers in a recent publication [19]. The proposed fragmentation pathways are helpful for characterization of new steroids. The approach used in this study for elucidation of the fragmentation pathways is helpful in interpretation of complicated product-ion spectra of other compounds, drugs and their metabolites. (J Am Soc Mass Spectrom 2006, 17, 477-489)

Detection and Characterization of a New Metabolite of 17α-Methyltestosterone

“…2, c and d). This finding is in agreement with a previous study stating that the addition of a double bond in the steroid structure results in a significantly different CID spectrum (Guan et al, 2006). To suggest a possible structure for A5 two zones of the spectrum were studied: the region close to the [M ϩ H] ϩ and the most abundant ions at 30 eV of collision energy.…”

Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion–Dipole Complex Intermediates

“…Although GC-MS approaches are highly sensitive, they have some limitations due to the need for multistep derivatization procedures for these thermally-labile compounds, especially those that contain large numbers of hydroxyl groups [9,30,31]. In recent years, ESI-MS has been widely used for steroid analysis [32][33][34]. Currently, LC coupled to ESI-MS [35][36][37], ESI-MS/MS, or APCI-MS [38] are the favored techniques to analyze steroid mixtures.…”

Isotope pattern evaluation for the reduction of elemental compositions assigned to high-resolution mass spectral data from electrospray ionization fourier transform ion cyclotron resonance mass spectrometry

“…etermination of elemental composition (EC) from high-accuracy mass measurement is a widely accepted method for gaining information on organic molecules determined in mass spectrometry [1,2]. In theory, every distinct elemental composition has a unique mass that permits unique identification of a compound just from this exact mass [3].…”