| Negative Ion CID Fragmentation of O-linked Oligosaccharide Aldoses-Charge Induced and Charge Remote Fragmentation. | |
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MedLine Citation:
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PMID: 21953046 Owner: NLM Status: In-Data-Review |
Abstract/OtherAbstract:
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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. |
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Authors:
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Roisin A Doohan; Catherine A Hayes; Brendan Harhen; Niclas Göran Karlsson |
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Publication Detail:
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Type: Journal Article Date: 2011-03-31 |
Journal Detail:
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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:
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Created Date: 2011-09-28 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9010412 Medline TA: J Am Soc Mass Spectrom Country: United States |
Other Details:
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Languages: eng Pagination: 1052-62 Citation Subset: IM |
Affiliation:
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School of Chemistry, National University of Ireland, Galway, Ireland. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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