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The influence of structural features on facile McLafferty‐type, even‐electron rearrangements in tandem mass spectra of carboxylate anions
Author(s) -
Grossert J. Stuart,
Cook Matthew C.,
White Robert L.
Publication year - 2006
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2506
Subject(s) - chemistry , carboxylate , tandem , ion , mass spectrometry , tandem mass spectrometry , mass spectrum , quadrupole , electron ionization , proton , analytical chemistry (journal) , crystallography , computational chemistry , stereochemistry , organic chemistry , ionization , atomic physics , chromatography , quantum mechanics , composite material , materials science , physics
In contrast to the well‐described McLafferty rearrangement in odd‐electron cations, relatively little has been reported on comparable rearrangements in even‐electron ions, especially negative ions. This work reports a systematic study using tandem mass spectrometry (MS/MS) fragment ion spectra of carboxylate anions having a suitably acidic proton in the γ position. The rearrangement process was studied in both ion trap and triple quadrupole mass spectrometers; characteristic enolate anions and stable neutral products were formed at low collision energies. The process has diagnostic and analytical potential in, for example, the analysis of peptides having C‐terminal serine residues and of 3‐hydroxy‐ or 3‐aminocarboxylic acids in complex mixtures. Copyright © 2006 John Wiley & Sons, Ltd.