Structure-fragmentation relationship and rapid dereplication of Buxus steroidal alkaloids by electrospray ionization-quadrupole time-of-flight mass spectrometry
Article first published online: 12 DEC 2012
Copyright © 2012 John Wiley & Sons, Ltd.
Rapid Communications in Mass Spectrometry
Volume 27, Issue 1, pages 169–178, 15 January 2013
How to Cite
Musharraf, S. G., Goher, M., Shahnaz, S., Choudhary, M. I. and Atta-ur-Rahman (2013), Structure-fragmentation relationship and rapid dereplication of Buxus steroidal alkaloids by electrospray ionization-quadrupole time-of-flight mass spectrometry. Rapid Commun. Mass Spectrom., 27: 169–178. doi: 10.1002/rcm.6441
- Issue published online: 21 NOV 2012
- Article first published online: 12 DEC 2012
- Manuscript Accepted: 16 OCT 2012
- Manuscript Revised: 14 OCT 2012
- Manuscript Received: 24 AUG 2012
Tandem mass spectrometric studies of natural products revealed the identification of key fragments which can be helpful for their rapid dereplication in plant extracts utilizing a liquid chromatography/tandem mass spectrometry (LC/MS/MS) approach, particularly for the thermally labile compounds. The knowledge of the collision-induced dissociation (CID) fragmentation pattern of the molecule is essentially required prior to the analysis by LC/MS/MS.
The fragmentation patterns of eleven Buxus steroidal alkaloids were studied by using a positive ion electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-QqTOF-MS/MS) hybrid instrument. Chromatographic separation of a Buxus papillosa extract was achieved using a capillary HPLC system coupled with the mass instrument.
ESI-QqTOF-MS (positive ion mode) showed the presence of several characteristic fragments which can be used to rapidly identify various classes of Buxus steroidal alkaloids. The presence of a cyclopropane ring in the cycloartenol skeleton and the hydroxyl group at C-10 was found to effect on the fragmentation pattern and afford characteristic peaks. This study distinguishes between different types of Buxus steroidal alkaloids based on logical fragmentation pathways. This strategy was successfully applied in LC/ESI-QqTOF-MS/MS analysis of Buxus papillosa extract to investigate and characterize Buxus steroidal alkaloids and 14 compounds were identified as steroidal alkaloids.
The knowledge of the fragmentation pattern was used for the rapid identification of this bioactive group of biosynthetically unique steroidal alkaloids in complex plant extracts of Buxus species, especially in the absence of any reference material, by combining key fragments, exact mass measurements and relative abundances of diagnostic fragment ions. Copyright © 2012 John Wiley & Sons, Ltd.