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Analysis and development of structure-fragmentation relationships in withanolides using an electrospray ionization quadropole time-of-flight tandem mass spectrometry hybrid instrument.
Rapid Commun Mass Spectrom. 2011 Jan 15; 25(1):104-14.RC

Abstract

Structural elucidation and gas-phase fragmentation of ten withanolides (steroidal lactones) were studied using a positive ion electrospray ionization quadropole time-of-flight mass spectrometry (ESI-QqTOF-MS/MS) hybrid instrument. Withanolides form an important class of plant secondary metabolites, known to possess a variety of biological activities. Withanolides which possess hydroxyl groups at C-4, C-5, C-17, C-20, and C-27, and an epoxy group at C-5/C-6, were evaluated to determine the characteristic fragments and their possible pathways. ESI-QqTOF-MS (positive ion mode) showed the presence of the protonated molecules [M + H](+) . Low-energy collision-induced dissociation tandem mass spectrometric (CID-MS/MS) analysis of the protonated molecule [M + H](+) indicated multiple losses of water and the removal of the C-17-substituted lactone moiety affording the [M + H-Lac](+) product ion as the predominant pathways. However, withanolides containing a hydroxyl group at C-24 of the lactone moiety showed a different fragmentation pathway, which include the loss of steroidal part as a neutral molecule, with highly diagnostic ions at m/z 95 and 67 being generated from the cleavage of lactone moiety. Our results also determined the influence of the presence and positions of hydroxyl and epoxy groups on product ion formation and stability. Moreover, the knowledge of the fragmentation pattern was utilized in rapid identification of withanolides by the LC/MS/MS analysis of a Withania somnifera extract.

Authors+Show Affiliations

H.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences (ICCBS), University of Karachi, Karachi-75270, Pakistan. musharraf1977@yahoo.comNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

21157859

Citation

Musharraf, Syed Ghulam, et al. "Analysis and Development of Structure-fragmentation Relationships in Withanolides Using an Electrospray Ionization Quadropole Time-of-flight Tandem Mass Spectrometry Hybrid Instrument." Rapid Communications in Mass Spectrometry : RCM, vol. 25, no. 1, 2011, pp. 104-14.
Musharraf SG, Ali A, Ali RA, et al. Analysis and development of structure-fragmentation relationships in withanolides using an electrospray ionization quadropole time-of-flight tandem mass spectrometry hybrid instrument. Rapid Commun Mass Spectrom. 2011;25(1):104-14.
Musharraf, S. G., Ali, A., Ali, R. A., Yousuf, S., Rahman, A. U., & Choudhary, M. I. (2011). Analysis and development of structure-fragmentation relationships in withanolides using an electrospray ionization quadropole time-of-flight tandem mass spectrometry hybrid instrument. Rapid Communications in Mass Spectrometry : RCM, 25(1), 104-14. https://doi.org/10.1002/rcm.4835
Musharraf SG, et al. Analysis and Development of Structure-fragmentation Relationships in Withanolides Using an Electrospray Ionization Quadropole Time-of-flight Tandem Mass Spectrometry Hybrid Instrument. Rapid Commun Mass Spectrom. 2011 Jan 15;25(1):104-14. PubMed PMID: 21157859.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Analysis and development of structure-fragmentation relationships in withanolides using an electrospray ionization quadropole time-of-flight tandem mass spectrometry hybrid instrument. AU - Musharraf,Syed Ghulam, AU - Ali,Arslan, AU - Ali,Rahat Azher, AU - Yousuf,Sammer, AU - Rahman,Atta-Ur-, AU - Choudhary,M Iqbal, PY - 2010/12/16/entrez PY - 2010/12/16/pubmed PY - 2011/4/1/medline SP - 104 EP - 14 JF - Rapid communications in mass spectrometry : RCM JO - Rapid Commun Mass Spectrom VL - 25 IS - 1 N2 - Structural elucidation and gas-phase fragmentation of ten withanolides (steroidal lactones) were studied using a positive ion electrospray ionization quadropole time-of-flight mass spectrometry (ESI-QqTOF-MS/MS) hybrid instrument. Withanolides form an important class of plant secondary metabolites, known to possess a variety of biological activities. Withanolides which possess hydroxyl groups at C-4, C-5, C-17, C-20, and C-27, and an epoxy group at C-5/C-6, were evaluated to determine the characteristic fragments and their possible pathways. ESI-QqTOF-MS (positive ion mode) showed the presence of the protonated molecules [M + H](+) . Low-energy collision-induced dissociation tandem mass spectrometric (CID-MS/MS) analysis of the protonated molecule [M + H](+) indicated multiple losses of water and the removal of the C-17-substituted lactone moiety affording the [M + H-Lac](+) product ion as the predominant pathways. However, withanolides containing a hydroxyl group at C-24 of the lactone moiety showed a different fragmentation pathway, which include the loss of steroidal part as a neutral molecule, with highly diagnostic ions at m/z 95 and 67 being generated from the cleavage of lactone moiety. Our results also determined the influence of the presence and positions of hydroxyl and epoxy groups on product ion formation and stability. Moreover, the knowledge of the fragmentation pattern was utilized in rapid identification of withanolides by the LC/MS/MS analysis of a Withania somnifera extract. SN - 1097-0231 UR - https://www.unboundmedicine.com/medline/citation/21157859/Analysis_and_development_of_structure_fragmentation_relationships_in_withanolides_using_an_electrospray_ionization_quadropole_time_of_flight_tandem_mass_spectrometry_hybrid_instrument_ L2 - https://doi.org/10.1002/rcm.4835 DB - PRIME DP - Unbound Medicine ER -