Journal
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
Volume 308, Issue 2-3, Pages 253-259Publisher
ELSEVIER
DOI: 10.1016/j.ijms.2011.08.029
Keywords
Glycosaminoglycans; Fourier transform mass spectrometry; Electron detachment dissociation; Infrared multiphoton dissociation
Funding
- National Institutes of Health [2R01-GM038060-16]
- University of Georgia Graduate School
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Heparin glycosaminoglycans (GAGs) present the most difficult glycoform for analytical characterization due to high levels of sulfation and structural heterogeneity. Recent contamination of the clinical heparin supply and subsequent fatalities has highlighted the need for sensitive methodologies of analysis. In the last decade, tandem mass spectrometry has been increasingly applied for the analysis of GAGs, but developments in the characterization of highly sulfated compounds have been minimal due to the low number of cross-ring cleavages generated by threshold ion activation by collisional induced dissociation (CID). In the current work, electron detachment dissociation (EDD) and infrared multiphoton dissociation (IRMPD) are applied to a series of heparin tetrasaccharides. With both activation methods, abundant glycosidic and cross-ring cleavages are observed. The concept of Ionized Sulfate Criteria (ISC) is presented as a succinct method for describing the charge state, degree of ionization and sodium/proton exchange in the precursor ion. These factors contribute to the propensity for useful fragmentation during MS/MS measurements. Precursors with ISC values of 0 are studied here, and shown to yield adequate structural information from ion activation by EDD or IRMPD. (C) 2011 Elsevier B.V. All rights reserved.
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