Collision-induced dissociation of xylose and its applications in linkage and anomericity identification

Abstract

Different dehydration barrier heights result in different branching ratio, a simple and fast anomeric configuration identification for xylose.

Differentiation of aldohexoses and ketohexoses through collision‐induced dissociation

“…[ 18 ] In the MS 2 CID spectra of lithium adducts (Figure 2b), the precursor ion is m/z 187, the product of dehydration is ion m/z 169, and products of cross‐ring dissociation are ions m/z 157 ( 0, 1 A), 127 ( 0, 2 A and 0, 4 X) and 97 ( 0, 3 A and 0, 3 X). In our previous studies of glucose, [ 19 ] galactose, mannose, [ 20 ] and xylose, [ 21 ] we have showed that the relative branching ratios of dehydration to cross‐ring dissociation for the anomer with O1 and O2 atoms in cis configuration are larger than that for the anomer in trans configuration. This dehydration propensity rule can be rationalized from the dissociation mechanism.…”

“…The cross‐ring dissociation mechanisms of aldohexose (glucose, galactose, mannose) and aldopentose (xylose) sodium and lithium adducts have been investigated in our previous studies. [ 19–21 ] Figure 3 shows the cross‐ring dissociation mechanism of aldohexose sodium (or lithium) adducts. The cross‐ring dissociation involves sequential reactions.…”

“…The similar phenomena that sodium‐ion elimination is the major dissociation channel but lithium‐ion elimination is the minor dissociation channel have been reported in our previous studies of xylose. [ 21 ]…”

Identification of Anomericity and Linkage of Arabinose and Ribose through Collision-Induced Dissociation

“…Identifying the arabinose and ribose structures in these polysaccharides is essential for understanding the corresponding biological processes. Although mass spectrometry is more sensitive than other methods (e.g., nuclear magnetic resonance spectroscopy) for identifying carbohydrate structures, differentiating stereoisomers (e.g., arabinose and ribose), anomericity (α- and β-configuration), and the ring form (furanose and pyranose) remains challenging. , We recently developed a novel mass spectrometry method, on the basis of the dissociation mechanisms, for the identification of linkages, anomericity, and stereoisomers of monosaccharides such as glucose, galactose, and mannose, − amino sugars, , and xylose . This method can be used for in situ identification of the monosaccharides produced from oligosaccharides through collision-induced dissociation (CID) inside mass spectrometers.…”

“…Except for amino sugars, all monosaccharide sodium adducts and lithium adducts have been found to possess the same major dissociation channels (i.e., dehydration and cross-ring cleavage) and similar dissociation mechanisms. However, only the pyranose forms of these monosaccharides have been studied; − no monosaccharides in furanose form have been studied. In this work, we examined the arabinose and ribose isomers through chromatography, CID mass spectra, quantum chemistry calculations, and transition state theory.…”