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Linkage Memory in Underivatized Protonated Carbohydrates

preprint
submitted on 05.08.2020 and posted on 10.08.2020 by Abhigya Mookherjee, Sanjit S. Uppal, Taylor A. Murphree, Miklos Guttman

Carbohydrates are among the most complex class of biomolecules and even subtle variations in their structures are attributed to diverse biological function. Mass spectrometry has been essential for large scale glycomics and glycoproteomics studies, but the gas-phase structures and sometimes anomalous fragmentation properties of carbohydrates present longstanding challenges. Here we investigate the gas-phase properties of a panel of isomeric protonated disaccharides differing in their linkage configurations. Multiple conformations were evident for most of the structures based on their fragment ion abundances by tandem mass spectrometry, their ion mobilities in several gases, and their deuterium uptake kinetics by gas-phase hydrogen deuterium exchange. Most notably, we find that the properties of the Y-ion fragments are characteristically influenced by the precursor carbohydrate’s linkage configuration. This study reveals how protonated carbohydrate fragment ions can retain ‘linkage memory’ that provides structural insight into their intact precursor.

History

Email Address of Submitting Author

abhigm@uw.edu

Institution

University of Washington

Country

United States

ORCID For Submitting Author

0000-0003-0897-8153

Declaration of Conflict of Interest

None

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