Spectroscopic Evidence for Mobilization of Amide Position Protons During CID of Model Peptide Ions

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.

Graphical AbstractInfrared multiple photon dissociation experiments suggest that amide-position protons are mobilized during fragmentation of a model peptide.Figure optionsDownload full-size imageDownload high-quality image (65 K)Download as PowerPoint slide