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 language | English |
|---|---|
| Pages (from-to) | 5390-5397 |
| Number of pages | 8 |
| Journal | Chemical Science |
| Volume | 7 |
| Issue number | 8 |
| DOIs | |
| State | Published - 1 Jan 2016 |
Fingerprint
Cite this
}
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 journal › Article
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 -