Intramolecular condensation reactions in protonated dipeptides: carbon monoxide, water, and ammonia losses in competition

Journal of the American Society for Mass Spectrometry
Francesco PingitoreBéla Paizs

Abstract

The elimination of carbon monoxide and water from a series of protonated dipeptides, [XxxYyy + H](+), is investigated by tandem mass spectrometry experiments and density functional theory. The combined results show that CO loss occurs on the a(1)-y(1) pathway, which begins by rearrangement of the added proton to the amide N-atom and creates the proton-bound dimer of an amino acid (Yyy) and an imine (that from Xxx residue). The loss of H(2)O is initiated from a tautomer in which the added proton has migrated to the hydroxyl group of the C-terminus, thereby promoting the formation of an ion with protonated oxazolone structure (a nominal b(2) ion). The highest yields of [XxxYyy + H - CO](+) and [XxxYyy + H - H(2)O](+) are observed at threshold energies. As the internal energy of the protonated dipeptides increases, these primary products are depleted by consecutive dissociations yielding mostly backbone fragments. Specifically, [XxxYyy + H - CO](+) decomposes to y(1) (protonated Yyy) and a(1) (immonium ion of Xxx residue), while [XxxYyy + H - H(2)O](+) produces a(2) and the immonium ions of residues Xxx (a(1)) and Yyy ("internal" immonium ion). Water loss takes place more efficiently when the more basic residue is at the C-termina...Continue Reading

References

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Citations

Sep 29, 2011·Journal of the American Society for Mass Spectrometry·P B Armentrout, Amy L Heaton
Sep 29, 2011·Journal of the American Society for Mass Spectrometry·P B Armentrout, Amy L Heaton
Nov 19, 2011·Journal of the American Society for Mass Spectrometry·Mathieu DupréChristine Enjalbal
Jun 5, 2007·Journal of the American Society for Mass Spectrometry·Richard D HiserodtCynthia J Mussinan
Oct 31, 2006·Journal of Mass Spectrometry : JMS·Laetitia MoulsChristine Enjalbal
Jul 15, 2011·Rapid Communications in Mass Spectrometry : RCM·Edgardo Rivera-Tirado, Chrys Wesdemiotis
May 9, 2012·Beilstein Journal of Organic Chemistry·Caterina FraschettiJochen Mattay
May 10, 2005·Journal of Mass Spectrometry : JMS
Jul 11, 2009·The Journal of Physical Chemistry. a·Bruno BottaMatthias C Letzel
Mar 15, 2005·Analytical Chemistry·Francesco Pingitore, Chrys Wesdemiotis
Mar 10, 2019·Journal of the American Society for Mass Spectrometry·A Mookherjee, P B Armentrout
Sep 13, 2018·Journal of the American Society for Mass Spectrometry·Pengyi ZhaoHao Chen
Oct 31, 2008·Journal of the American Society for Mass Spectrometry·Adrian K Y LamRichard A J O'Hair

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