High-energy collision-induced dissociation of oxosteroids derivatised to Girard hydrazones

Eur. J. Mass Spectrom. 10, 63–88 (2004)
DOI: 10.1255/ejms.625

High-energy collision-induced dissociation of oxosteroids derivatised to Girard hydrazones

William J. Griffiths^*
Department of Pharmaceutical & Biological Chemistry, The School of Pharmacy, University of London, 29-39 Brunswick Square, London WC1N 1AX, UK and Department of Medical Biochemistry & Biophysics, Karolinska Institutet, SE-17177 Stockholm, Sweden. E-mail: william.griffiths@ulsop.ac.uk
Gunvor Alvelius, Suya Liu and Jan Sjövall
Department of Medical Biochemistry & Biophysics, Karolinska Institutet, SE-17177 Stockholm, Sweden

ABSTRACT:

Neutral oxosteroids have been derivatised with Girard T and P hydrazine reagents to give the corresponding Girard hydrazone quaternary ammonium salts. Both Girard T (GT) and Girard P (GP) hydrazones of oxosteroids give very intense [M]⁺ ion signals in electrospray (ES) mass spectra and fragment within the ES interface and collision cell to give characteristic fragment ions. GT and GP derivatives give informative high-energy collision-induced dissociation spectra, from which the structure of the precursor oxosteroid can be determined. Both charge-remote and charge-mediated mechanisms are responsible for the formation of the fragment ions at high collision-energy.

Keywords: steroids, electrospray, tandem mass spectrometry, derivatisation, fragmentation mechanism

You can buy this paper on-line in PDF format; it costs only £11.75. Just click on the BUY on-line button. You can pay on-line through a secure server and get access immediately.