Dissociation reactions of protonated anthracycline antibiotics following electrospray ionization-tandem mass spectrometry

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DOIResolve DOI: http://doi.org/10.1016/j.ijms.2006.02.003
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TypeArticle
Journal titleInternational Journal of Mass Spectrometry
ISSN1387-3806
Volume255-256
Pages130138; # of pages: 9
Subjectanthracycline antibiotic; doxorubicin; fragmentation mechanism; tandem mass spectrometry; computational chemistry
AbstractFragmentation pathways of doxorubicin, a common cancer therapy agent, and three closely related analogs (epirubicin, daunorubicin, idarubicin) were compared using electrospray ionization with tandem mass spectrometry. This class of antibiotics with anti-tumour activity has important structural features, with a tetracyclic aromatic, polyketide portion, which is glycosylated with an amino sugar in order to exhibit its biological activity. Collision-induced dissociation spectra revealed very similar product ions for each analog, however, important differences were seen in the relative abundances and the ease at which certain fragments were formed. Fragment ions observed included those from cleavage of the glycosidic bond, loss of the side chain from the aglycone moiety, water losses and loss of a methyl radical. Following cleavage of the glycosidic bond, the charge can either reside on the aglycone portion or the sugar moiety, and each of these primary fragments undergoes several secondary dissociation pathways, depending on the collision energy. By ramping the collision voltage, we were able to correlate the changes in fragmentation behavior with small alterations in the structure of the precursor ion. The detailed study of the fragmentation behavior of doxorubicin was supported by accurate mass measurements, using an electrospray-time of flight instrument, as well as MS3 data from a quadrupole-linear ion trap mass spectrometer. Computational studies were also performed to help explain the role of certain functional groups in the fragmentation reactions.
Publication date
PublisherElsevier
Copyright noticeCopyright © 2006 Elsevier B.V. All rights reserved.
LanguageEnglish
AffiliationNRC Institute for Marine Biosciences; National Research Council Canada
Peer reviewedYes
NRC number55860
1620
NPARC number3538323
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Record identifieredcbf3a9-ca46-4ac8-a401-fc3e56502510
Record created2009-03-01
Record modified2016-05-09
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