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Negative Ion CID Fragmentation of O-linked Oligosaccharide Aldoses-Charge Induced and Charge Remote Fragmentation.
MedLine Citation:
PMID:  21953046     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
Collision induced dissociation (CID) fragmentation was compared between reducing and reduced sulfated, sialylated, and neutral O-linked oligosaccharides. It was found that fragmentation of the [M - H](-) ions of aldoses with acidic residues gave unique Z-fragmentation of the reducing end GalNAc containing the acidic C-6 branch, where the entire C-3 branch was lost. This fragmentation pathway, which is not seen in the alditols, showed that the process involved charge remote fragmentation catalyzed by a reducing end acidic anomeric proton. With structures containing sialic acid on both the C-3 and C-6 branch, the [M - H](-) ions were dominated by the loss of sialic acid. This fragmentation pathway was also pronounced in the [M - 2H](2-) ions revealing both the C-6 Z-fragment plus its complementary C-3 C-fragment in addition to glycosidic and cross ring fragmentation. This generation of the Z/C-fragment pairs from GalNAc showed that the charges were not participating in their generation. Fragmentation of neutral aldoses showed pronounced Z-fragmentation believed to be generated by proton migration from the C-6 branch to the negatively charged GalNAc residue followed by charge remote fragmentation similar to the acidic oligosaccharides. In addition, A-type fragments generated by charge induced fragmentation of neutral oligosaccharides were observed when the charge migrated from C-1 of the GalNAc to the GlcNAc residue followed by rearrangement to accommodate the (0,2)A-fragmentation. LC-MS also showed that O-linked aldoses existed as interchangeable α/β pyranose anomers, in addition to a third isomer (25% of the total free aldose) believed to be the furanose form.
Authors:
Roisin A Doohan; Catherine A Hayes; Brendan Harhen; Niclas Göran Karlsson
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Publication Detail:
Type:  Journal Article     Date:  2011-03-31
Journal Detail:
Title:  Journal of the American Society for Mass Spectrometry     Volume:  22     ISSN:  1879-1123     ISO Abbreviation:  J. Am. Soc. Mass Spectrom.     Publication Date:  2011 Jun 
Date Detail:
Created Date:  2011-09-28     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9010412     Medline TA:  J Am Soc Mass Spectrom     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1052-62     Citation Subset:  IM    
Affiliation:
School of Chemistry, National University of Ireland, Galway, Ireland.
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