Affordable Access

deepdyve-link
Publisher Website

The potential use of complex derivatization procedures in comprehensive HPLC-MS/MS detection of anabolic steroids.

Authors
  • Baranov, Pavel A
  • Appolonova, Svetlana A
  • Rodchenkov, Grigory M
Type
Published Article
Journal
Drug Testing and Analysis
Publisher
Wiley (John Wiley & Sons)
Publication Date
Oct 01, 2010
Volume
2
Issue
10
Pages
475–488
Identifiers
DOI: 10.1002/dta.163
PMID: 20878897
Source
Medline
License
Unknown

Abstract

The use of two separate derivatization procedures with the formation of oxime (hydroxyl ammonium pretreatment) and picolinoyl (mixed anhydride method) derivates of anabolic steroids following HPLC-MS/MS analysis was proposed. The main product ions of obtained derivatives for 21 anabolic steroids were evaluated and fragmentation pathways were compared.The analysis of MS/MS spectra for underivatized steroids versus oxime or picolinoyl derivatives showed that in case of analytes containing conjugated double bonds in sterane core all of the observed MS/MS spectra contained abundant product ions of diagnostic value. The implementation of derivatization procedures to such compounds is useful for upgrading sensitivity or selectivity of the evaluated method. On the other hand, MS/MS spectra of underivatized and oxime analytes without conjugated double bonds in sterane core produce spectra with large amounts of low abundant product ions. Picolinoyl derivatives formation leads to highly specific spectra with product ions of diagnostic value coupled with sensitive and selective analysis at the same time. The intra- and inter-group comparison analysis revealed that fragmentation pathways for underivatized steroids and correspondent oxime derivatives are similar.The obtained oxime and picolinoyl derivatives provided 10-15 times higher ESI response in the HPLC-ESI-MS-selected reaction monitoring (SRM) when compared to those of underivatized molecules in positive HPLC-ESI-MS mode.Due to the laborious sample preparation we suggest to use the performed strategy for confirmation analysis purposes, metabolic studies or while the identification of new steroids or steroid-like substances.

Report this publication

Statistics

Seen <100 times