Spectroscopic evidence for mobilization of amide position protons during CID of model peptide ions

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Molesworth, Samuel P.
Leavitt, Christopher M.
Groenewold, Gary S.
Oomens, Jos
Steill, Jeffrey D.
Van Stipdonk, Michael J.

Journal of the American Society for Mass Spectrometry. 2009 Oct; 20(10): 1841-5.


Infrared multiple photon dissociation (IRMPD) spectroscopy was used to study formation of b2+ from nicotinyl-glycine-glycine-methyl ester (NicGGOMe). IRMPD shows that NicGGOMe is protonated at the pyridine ring of the nicotinyl group, and more importantly, that b2+ from NicGGOMe is not protonated at the oxazolone ring, as would be expected if the species were generated on the conventional bn+/yn+ oxazolone pathway, but at the pyridine ring instead. IRMPD data support a hypothesis that formation of b2+ from NicGGOMe involves mobilization and transfer of an amide position proton during the fragmentation reaction.

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