Composition, Sequencing and Ion Mobility Mass Spectrometry of Heparan Sulfate-like Octasaccharide Isomers Differing in Glucuronic and Iduronic Acid Content. Issue 3 (June 2015)

• Record Type: Journal Article
• Authors: Miller, Rebecca L.; Wei, Wei; Schwörer, Ralf; Zubkova, Olga V.; Tyler, Peter C.; Turnbull, Jeremy E.; Leary, Julie A.
• Is Part Of: European journal of mass spectrometry. Volume 21:Issue 3(2015)
• Page Start: 245
• Page End: 254
• Publication Date: 2015-06
• Subjects: glycosaminoglycan -- heparan sulfate -- IMMS -- MS2 -- electron detachment dissociation -- arrival time distribution -- glucuronic acid -- iduronic acid; Mass spectrometry -- Periodicals; Mass Spectrometry; Mass spectrometry; Periodicals; Periodicals; 543.6505
• DOI: 10.1255/ejms.1337
• Languages: English
• ISSNs: 1469-0667

Abstract

Here we report ion mobility mass spectrometry (IMMS) separation and tandem mass spectrometry (MS 2 ) sequencing methods used to analyze and differentiate six synthetically produced heparin/heparan sulfate (HS)-like octasaccharide (dp8) isomeric structures. These structures are isomeric with regard to either glucuronic acid (GlcA) or iduronic acid (IdoA) residues at various positions. IMMS analysis showed that a fully GlcA structure exhibited a more compact conformation, whereas the fully IdoA structure was more extended. Interestingly, the change from IdoA to GlcA in specific locations resulted in strong conformational distortions. MS 2 of the six isomers showed very different spectra with unique sets of diagnostic product ions. Analysis of MS 2 product ion spectra suggests that the GlcA group correlated with the formation of a glycosidic product ion under lower energy conditions. This resulted in an earlier product ion formation and more intense product ions. Importantly, this knowledge enabled a complete sequencing of the positions of GlcA and IdoA in each of the four positions located in each unique dp8 structure.