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Mass spectrometric analysis of androstan-17β-ol-3-one and androstadiene-17β-ol-3-one isomers

  • Mario Thevis
    Mario Thevis
    Institute of Biochemistry, German Sport University Cologne, Carl-Diem Weg 6, 50933, Cologne, Germany
    More by Mario Thevis
  •  and 
  • Wilhelm Schänzer
    Wilhelm Schänzer
    Institute of Biochemistry, German Sport University Cologne, Carl-Diem Weg 6, 50933, Cologne, Germany
Cite this: J Am Soc Mass Spectrom 2005, 16, 10, 1660–1669
Publication Date (Web):October 1, 2005
https://doi.org/10.1016/j.jasms.2005.06.007
Copyright © 2005 © American Society for Mass Spectrometry 2005

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    Abstract

    Mass spectrometric identification and characterization of steroids using electrospray ionization and tandem mass spectrometry has advantages in drug testing and doping control analysis attributable to limitations of gas chromatography followed by electron ionization mass spectrometry. Steroids with an androstadiene-17β-ol-3-one nucleus and double bonds located either at C-1 and C-4, C-4 and C-9, or C-4 and C-6 were used to determine characteristic fragmentation pathways. Diagnostic dissociation routes are proposed using deuterium labeling, MS3 experiments, and analyses of structurally closely related compounds. Steroids such as boldenone (androst-1,4-diene-17β-ol-3-one) produced characteristic product ions at m/z 121, 135, and 147. Compounds with double bonds at C-4 and C-9 generated abundant product ions at m/z 145 and 147. Conjugated double bonds at C-4 and C-6 gave rise to an intense and characteristic signal at m/z 133. Stereochemical differentiation between 5α- and 5β-isomers of androstan-17β-ol-3-ones was possible because of significant differences in relative abundance of product ions generated by elimination of acetone from α,β-saturated 3-keto steroids.

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