Protonated α- N -Acetyl Galactose Glycopeptide Dissociation Chemistry - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Journal of The American Society for Mass Spectrometry Année : 2022

Protonated α- N -Acetyl Galactose Glycopeptide Dissociation Chemistry

Résumé

We recently provided mass spectrometric, H/D labeling, and computational evidence of pyranose to furanose N-Acetylated ion isomerization reactions occurring prior to glycosidic bond cleavage in both O-and N-linked glycosylated amino acid model systems (Phys. Chem. Chem. Phys., 2021, 23, 23256-23266). These reactions occurred irrespective of glycosidic linkage stereochemistry (α/β) and N-Acetylated hexose structure (GlcNAc/GalNAc). In the present article we test the generality of the preceding findings by examining Threonyl α-GalNAc glycosylated peptides. We utilize computational chemistry to compare the various dissociation and isomerization pathways accessible with collisional activation. We then interrogate the structure(s) of the resulting charged glycan and peptide fragments with infrared "action" spectroscopy. Isomerization of the original pyranose, protonated glycopeptide, [AT(GalNAc)A+H] + , is predicted to be facile compared to direct dissociation, as is glycosidic bond cleavage of the newly formed furanose form. i.e., furanose oxazolinium ion structures are predicted to predominate. IR action spectra for the m/z 204, C8H14N1O5 + , glycan fragment population support this prediction. The IR action spectra of the complementary m/z 262, peptide fragment are assigned as a mixture of the lowest energy structures of [ATA+H] + consistent with the literature. If general, the change to a furanose m/z 204 product ion structure fundamentally alters the ion population available for MS 3 dissociation and glycopeptide sequence identification.

Domaines

Chimie
Fichier principal
Vignette du fichier
ATgalnacA_8_11_22_JASMS_R2_final.pdf (1.52 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03873726 , version 1 (27-11-2022)

Identifiants

Citer

Jordan Rabus, Shanshan Guan, Lauren Schultz, Maha Abutokaikah, Philippe Maître, et al.. Protonated α- N -Acetyl Galactose Glycopeptide Dissociation Chemistry. Journal of The American Society for Mass Spectrometry, 2022, 33 (9), pp.1745-1752. ⟨10.1021/jasms.2c00155⟩. ⟨hal-03873726⟩
6 Consultations
68 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More