ELECTRON DETACHMENT DISSOCIATION AND INFRARED MULTIPHOTON DISSOCIATION OF HEPARIN TETRASACCHARIDES.

ELECTRON DETACHMENT DISSOCIATION AND INFRARED MULTIPHOTON DISSOCIATION OF HEPARIN TETRASACCHARIDES.
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DOI:
10.1016/j.ijms.2011.08.029
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发表时间:
2011-12-01
影响因子:
1.8
通讯作者:
Amster IJ
Amster IJ
中科院分区:
化学4区
文献类型:
--
作者:
Leach FE 3rd;Xiao Z;Laremore TN;Linhardt RJ;Amster IJ

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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.
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