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Composition, sequencing and ion mobility mass spectrometry of heparan sulfatelike octasaccharide isomers differing in glucuronic and iduronic acid content

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posted on 18.11.2021, 20:15 by RL Miller, W Wei, Ralf SchwoererRalf Schwoerer, Olga ZubkovaOlga Zubkova, Peter TylerPeter Tyler, JE Turnbull, JA Leary
Here we report ion mobility mass spectrometry (IMMS) separation and tandem mass spectrometry (MS2) 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. MS2 of the six isomers showed very different spectra with unique sets of diagnostic product ions. Analysis of MS2 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.

History

Preferred citation

Miller, R. L., Wei, W., Schwörer, R., Zubkova, O. V., Tyler, P. C., Turnbull, J. E. & Leary, J. A. (2015). Composition, sequencing and ion mobility mass spectrometry of heparan sulfatelike octasaccharide isomers differing in glucuronic and iduronic acid content. European Journal of Mass Spectrometry, 21(3), 245-254. https://doi.org/10.1255/ejms.1337

Journal title

European Journal of Mass Spectrometry

Volume

21

Issue

3

Publication date

14/05/2015

Pagination

245-254

Publisher

SAGE Publications

Publication status

Published

Contribution type

Article

Online publication date

01/06/2015

ISSN

1469-0667

eISSN

1751-6838

Language

en