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Study of the gas-phase fragmentation behaviour of sulfonatedpeptides

Škulj, Sanja; Rožman, Marko (2015) Study of the gas-phase fragmentation behaviour of sulfonatedpeptides. International Journal of Mass Spectrometry, 391 . pp. 11-16. ISSN 1387-3806

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Abstract

A series of singly and doubly protonated peptides bearing sulfonated residue have been studied, usingboth experiment and molecular modelling, to elucidate fragmentation chemistry of sulfonated peptides.Collision-induced dissociation mass spectra indicate that the sulfo group loss (neutral loss of 80 Da) isthe dominant dissociation channel. Modelling results suggest the proton transfer mechanism, whereupon vibrational excitation, the acidic side chain proton is transferred from the sulfo group hydroxyl tothe ester oxygen resulting in S O bond cleavage and formation of the unmodified hydroxyl containingresidue and SO3. Conformations associated with potential energy profile of the reaction imply the chargeremote nature of the proposed mechanism. The proposed proton transfer mechanism was compared withthe intramolecular nucleophilic substitution (SN2) mechanism, the main pathway suggested for neutralloss of phosphoric acid from phosphopeptides. Both pathways (proton transfer and SN2) are available forsulfonated and phosphorylated peptides ; however, each posttranslational modification favours differentmechanism. The change of the bond dissociation enthalpies and the ability of stabilising the transitionstate structures are demonstrated as main factors responsible for each posttranslational modificationactivating a different pathway.

Item Type: Article
Uncontrolled Keywords: Posttranslational modifications; Sulfonation; Collision-induced dissociation; Fragmentation mechanism; Molecular modelling
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Physical Chemistry
Depositing User: Kristina Ciglar
Date Deposited: 17 Jan 2017 10:10
Last Modified: 30 Nov 2017 00:15
URI: http://fulir.irb.hr/id/eprint/3320
DOI: 10.1016/j.ijms.2015.07.023

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