Eradicating mass spectrometric glycan rearrangement by utilizing free radicals

Nikunj Desai, Daniel A. Thomas, Jungeun Lee, Jinshan Gao, J. L. Beauchamp

Research output: Contribution to journalArticle

7 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)5390-5397
Number of pages8
JournalChemical Science
Volume7
Issue number8
DOIs
StatePublished - 1 Jan 2016

Fingerprint

Free Radicals
Polysaccharides
Chemical activation
Blueprints
Ions

Cite this

Desai, Nikunj ; Thomas, Daniel A. ; Lee, Jungeun ; Gao, Jinshan ; Beauchamp, J. L. / Eradicating mass spectrometric glycan rearrangement by utilizing free radicals. In: Chemical Science. 2016 ; Vol. 7, No. 8. pp. 5390-5397.
@article{bc4f85e422e4430f897c5d3fdbaca05b,
title = "Eradicating mass spectrometric glycan rearrangement by utilizing free radicals",
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.",
author = "Nikunj Desai and Thomas, {Daniel A.} and Jungeun Lee and Jinshan Gao and Beauchamp, {J. L.}",
year = "2016",
month = "1",
day = "1",
doi = "10.1039/c6sc01371f",
language = "English",
volume = "7",
pages = "5390--5397",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "8",

}

Eradicating mass spectrometric glycan rearrangement by utilizing free radicals. / Desai, Nikunj; Thomas, Daniel A.; Lee, Jungeun; Gao, Jinshan; Beauchamp, J. L.

In: Chemical Science, Vol. 7, No. 8, 01.01.2016, p. 5390-5397.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Eradicating mass spectrometric glycan rearrangement by utilizing free radicals

AU - Desai, Nikunj

AU - Thomas, Daniel A.

AU - Lee, Jungeun

AU - Gao, Jinshan

AU - Beauchamp, J. L.

PY - 2016/1/1

Y1 - 2016/1/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84979649645&partnerID=8YFLogxK

U2 - 10.1039/c6sc01371f

DO - 10.1039/c6sc01371f

M3 - Article

AN - SCOPUS:84979649645

VL - 7

SP - 5390

EP - 5397

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 8

ER -