Open AccessLinkage Memory in Underivatized Protonated Carbohydrates
Author(s) -
Abhigya Mookherjee,
Sanjit S. Uppal,
Taylor A. Murphree,
Miklós Guttman
Publication year - 2020
Publication title -
journal of the american society for mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.961
H-Index - 127
eISSN - 1879-1123
pISSN - 1044-0305
DOI - 10.1021/jasms.0c00440
Subject(s) - chemistry , glycoproteomics , glycomics , protonation , mass spectrometry , tandem mass spectrometry , biomolecule , fragmentation (computing) , deuterium , ion , hydrogen–deuterium exchange , glycan , chromatography , organic chemistry , biochemistry , physics , quantum mechanics , computer science , glycoprotein , operating system
Carbohydrates are among the most complex class of biomolecules, and even subtle variations in their structures are attributed to diverse biological functions. 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 long-standing 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.