Characterization of chemically modified steroids for doping control purposes by electrospray ionization tandem mass spectrometry
Article first published online: 15 FEB 2005
Copyright © 2005 John Wiley & Sons, Ltd.
Journal of Mass Spectrometry
Volume 40, Issue 4, pages 494–502, April 2005
How to Cite
Thevis, M., Bommerich, U., Opfermann, G. and Schänzer, W. (2005), Characterization of chemically modified steroids for doping control purposes by electrospray ionization tandem mass spectrometry. J. Mass Spectrom., 40: 494–502. doi: 10.1002/jms.820
- Issue published online: 18 APR 2005
- Article first published online: 15 FEB 2005
- Manuscript Accepted: 8 DEC 2004
- Manuscript Received: 19 OCT 2004
- Manfred-Donike Society.
- designer steroids;
- electrospray ionization;
- mass spectrometry;
The discovery of the designer steroid tetrahydrogestrinone (THG) in elite athletes' doping control samples in 2003 demonstrated the availability of steroid derivatives prepared solely for doping purposes. Modern mass spectrometers utilizing electrospray ionization and collisionally activated dissociation (CAD) of analytes allow the structural characterization of steroids and their derivatization sites by the elucidation of fragmentation behaviors. A total of 21 steroids comprising either a 4,9,11-triene, a 3-keto-4-ene or a 3-keto-1-ene nucleus were investigated regarding their dissociation pathways, deuterated analogues were synthesized and fragmentation routes were postulated, permitting the identification of steroidal structures and modifications. Compounds based on a 4,9,11-triene steroid with an ethyl residue at C-13 (gestrinone analogues) generate abundant fragment ions at m/z 241 and 199, whereas the substitution of the C-13 ethyl group by a methyl residue (trenbolone analogues) results in a shift of m/z 241 to 227. Substances related to testosterone with a 3-keto-4-ene structure give rise to abundant fragment ions at m/z 109 and 97 whereas steroids with a 3-keto-1-ene nucleus eliminate the A-ring including the carbons C-1–C-4, in addition to C-19 that is proposed to migrate from C-10 to C-1 under CAD conditions. Copyright © 2005 John Wiley & Sons, Ltd.