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Peptides derivatized with bicyclic quaternary ammonium ionization tags. Sequencing via tandem mass spectrometry
Authors:Bartosz Setner  Magdalena Rudowska  Ewelina Klem  Marek Cebrat  Zbigniew Szewczuk
Affiliation:Faculty of Chemistry, University of Wroc?aw, , 50‐383 Wroc?aw, Poland
Abstract:Improving the sensitivity of detection and fragmentation of peptides to provide reliable sequencing of peptides is an important goal of mass spectrometric analysis. Peptides derivatized by bicyclic quaternary ammonium ionization tags: 1‐azabicyclo2.2.2]octane (ABCO) or 1,4‐diazabicyclo2.2.2]octane (DABCO), are characterized by an increased detection sensitivity in electrospray ionization mass spectrometry (ESI‐MS) and longer retention times on the reverse‐phase (RP) chromatography columns. The improvement of the detection limit was observed even for peptides dissolved in 10 mM NaCl. Collision‐induced dissociation tandem mass spectrometry of quaternary ammonium salts derivatives of peptides showed dominant a‐ and b‐type ions, allowing facile sequencing of peptides. The bicyclic ionization tags are stable in collision‐induced dissociation experiments, and the resulted fragmentation pattern is not significantly influenced by either acidic or basic amino acid residues in the peptide sequence. Obtained results indicate the general usefulness of the bicyclic quaternary ammonium ionization tags for ESI‐MS/MS sequencing of peptides. Copyright © 2014 John Wiley & Sons, Ltd.
Keywords:derivatization of peptides  peptide sequencing  DABCO  ABCO
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