The Competition of Charge Remote and Charge Directed Fragmentation Mechanisms in Quaternary Ammonium Salt Derivatized Peptides—An Isotopic Exchange StudyReport as inadecuate




The Competition of Charge Remote and Charge Directed Fragmentation Mechanisms in Quaternary Ammonium Salt Derivatized Peptides—An Isotopic Exchange Study - Download this document for free, or read online. Document in PDF available to download.

Journal of The American Society for Mass Spectrometry

, Volume 22, Issue 12, pp 2103–2107

First Online: 05 October 2011Received: 20 June 2011Revised: 26 August 2011Accepted: 31 August 2011

Abstract

Derivatization of peptides as quaternary ammonium salts QAS is a promising method for sensitive detection by electrospray ionization tandem mass spectrometry Cydzik et al. J. Pept. Sci.2011, 17, 445–453. The peptides derivatized by QAS at their N-termini undergo fragmentation according to the two competing mechanisms – charge remote ChR and charge directed ChD. The absence of mobile proton in the quaternary salt ion results in ChR dissociation of a peptide bond. However, Hofmann elimination of quaternary salt creates an ion with one mobile proton leading to the ChD fragmentation. The experiments on the quaternary ammonium salts with deuterated N-alkyl groups or amide NH bonds revealed that QAS derivatized peptides dissociate according to the mixed ChR-ChD mechanism. The isotopic labeling allows differentiation of fragments formed according to ChR and ChD mechanisms.

Key wordsQuaternary ammonium salts Derivatization of peptides Peptide sequencing Electronic supplementary materialThe online version of this article doi:10.1007-s13361-011-0245-2 contains supplementary material, which is available to authorized users.

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Author: Marzena Cydzik - Magdalena Rudowska - Piotr Stefanowicz - Zbigniew Szewczuk

Source: https://link.springer.com/







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