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Issue 8, 2016
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Eradicating mass spectrometric glycan rearrangement by utilizing free radicals

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Abstract

Mass spectrometric glycan rearrangement is problematic because it provides misleading structural information. Here we report on a new reagent, a methylated free radical activated glycan sequencing reagent (Me-FRAGS), which combines a free radical precursor with a methylated pyridine moiety that can be coupled to the reducing terminus of glycans. The collisional activation of Me-FRAGS-derivatized glycans generates a nascent free radical that concurrently induces abundant glycosidic bond and cross-ring cleavage without the need for subsequent activation. The product ions resulting from glycan rearrangement, including internal residue loss and multiple external residue losses, are precluded. Glycan structures can be easily assembled and visualized using a radical driven glycan deconstruction diagram (R-DECON diagram). The presence and location of N-acetylated saccharide units and branch sites can be identified from the characteristic dissociation patterns observed only at these locations. The mechanisms of dissociation are investigated and discussed. This Me-FRAGS based mass spectrometric approach creates a new blueprint for glycan structure analysis.

Graphical abstract: Eradicating mass spectrometric glycan rearrangement by utilizing free radicals

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Supplementary files

Article information


Submitted
28 Mar 2016
Accepted
04 May 2016
First published
05 May 2016

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 5390-5397
Article type
Edge Article

Eradicating mass spectrometric glycan rearrangement by utilizing free radicals

N. Desai, D. A. Thomas, J. Lee, J. Gao and J. L. Beauchamp, Chem. Sci., 2016, 7, 5390
DOI: 10.1039/C6SC01371F

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