Abstract
The fragmentation reactions of isomeric dipeptides containing α- and β-alanine residues (αAla-αAla, αAla-βAla, βAla-αAla, and βAla-βAla) were studied using a combination of low-energy and energy resolved collision induced dissociation (CID). Each dipeptide gave a series of different fragment ions, allowing for differentiation. For example, peptides containing an N-terminal β-Ala residue yield a diagnostic imine loss, while lactam ions at m/z 72 are unique to peptides containing β-Ala residues. In addition, MS3 experiments were performed. Structure-specific fragmentation reactions were observed for y1 ions, which help identify the C-terminal residue. The MS3 spectra of the b2 ions are different suggesting they are unique for each peptide. Density functional theory (DFT) calculations predict that b2 ions formed via a neighboring group attack by the amide are thermodynamically favored over those formed via neighboring group attack by the N-terminal amine. Finally, to gain further insight into the unique fragmentation chemistry of the peptides containing an N-terminal β-alanine residue, the fragmentation reactions of protonated β-Ala-NHMe were examined using a combination of experiment and DFT calculations. The relative transition-state energies involved in the four competing losses (NH3, H2O, CH3NH2, and CH2=NH) closely follow the relative abundances of these as determined via CID experiments.
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Published online September 12, 2008
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Lam, A.K.Y., Ramarathinam, S.H., Purcell, A.W. et al. Can α- and β-alanine containing peptides Be distinguished based on the CID spectra of their protonated ions?. J Am Soc Mass Spectrom 19, 1743–1754 (2008). https://doi.org/10.1016/j.jasms.2008.09.007
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DOI: https://doi.org/10.1016/j.jasms.2008.09.007