dc.contributor.author | Doohan, Roisin A. | |
dc.contributor.author | Hayes, Catherine A. | |
dc.contributor.author | Harhen, Brendan | |
dc.contributor.author | Karlsson, Niclas Göran | |
dc.date.accessioned | 2018-09-20T16:06:23Z | |
dc.date.available | 2018-09-20T16:06:23Z | |
dc.date.issued | 2011-03-31 | |
dc.identifier.citation | Doohan, Roisin A. Hayes, Catherine A.; Harhen, Brendan; Karlsson, Niclas Göran (2011). Negative ion cid fragmentation of o-linked oligosaccharide aldoses—charge induced and charge remote fragmentation. Journal of The American Society for Mass Spectrometry 22 (6), 1052-1062 | |
dc.identifier.issn | 1044-0305,1879-1123 | |
dc.identifier.uri | http://hdl.handle.net/10379/11234 | |
dc.description.abstract | 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 alpha/beta pyranose anomers, in addition to a third isomer (25% of the total free aldose) believed to be the furanose form. | |
dc.publisher | Springer Nature | |
dc.relation.ispartof | Journal of The American Society for Mass Spectrometry | |
dc.rights | Attribution-NonCommercial-NoDerivs 3.0 Ireland | |
dc.rights.uri | https://creativecommons.org/licenses/by-nc-nd/3.0/ie/ | |
dc.subject | glycomics | |
dc.subject | mass spectrometry | |
dc.subject | electrospray | |
dc.subject | o-linked oligosaccharides | |
dc.subject | liquid chromatography/mass spectrometry | |
dc.subject | electrospray mass-spectrometry | |
dc.subject | alkaline borohydride treatment | |
dc.subject | carbohydrate microarrays | |
dc.subject | sulfated oligosaccharides | |
dc.subject | part 1 | |
dc.subject | glycoproteins | |
dc.subject | glycosylation | |
dc.subject | glycans | |
dc.subject | mucin | |
dc.title | Negative ion cid fragmentation of o-linked oligosaccharide aldoses—charge induced and charge remote fragmentation | |
dc.type | Article | |
dc.identifier.doi | 10.1007/s13361-011-0102-3 | |
dc.local.publishedsource | https://link.springer.com/content/pdf/10.1007%2Fs13361-011-0102-3.pdf | |
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