Electron detachment dissociation and infrared multiphoton dissociation of heparin tetrasaccharides

Leach, Franklin E.
Xiao, Zhongping
Laremore, Tatiana N.
Linhardt, Robert J.
Amster, I. Jonathan
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Biology , Chemistry and chemical biology , Chemical and biological engineering , Biomedical engineering
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Electron detachment dissociation and infrared multiphoton dissociation of heparin tetrasaccharides, F. E. Leach, Z. Xiao, T. N. Laremore, R. J. Linhardt, I. J. Amster, International Journal of Mass Spectrometry, 308, 253-259, 2011.
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.
International Journal of Mass Spectrometry, 308, 253-259
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The Linhardt Research Labs.
The Shirley Ann Jackson, Ph.D. Center for Biotechnology and Interdisciplinary Studies (CBIS)
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Rensselaer Polytechnic Institute, Troy, NY
International Journal of Mass Spectrometry
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