Abstract
We report a new fragmentation pathway for the CID of (b3−1+Cat)+ product ions derived from the model peptide AXAG, where X=β-alanine, γ-aminobutyric acid, ɛ-amino-n-caproic acid, or 4-aminomethylbenzoic acid. By changing the amino acid to the C-terminal side of the amino acid X, and incorporating 15N and 13C labeled residues at the same position, we conclude that the dissociation pathway most likely leads to a metal cationized nitrile. With respect to the various amino acids at position X, the putative nitrile product becomes more prominent, relative to the conventional (a3−1+Cat)+ species, in the order β-alanine<γ-aminobutyric acid<ɛ-aminocaproic acid<4-aminomethylbenzoic acid. The pathway is not observed for peptides with α-amino acids at position X. The product ion is observed most prominently during the CID of Li+ and Na+ cationized peptides, only to a small extent for Ag+ cationized peptides, and not at all from protonated analogues.
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Published online June 28, 2005
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Cooper, T.J., Talaty, E.R. & Van Stipdonk, M.J. Novel fragmentation pathway for CID of (bn−1+Cat)+ ions from model, metal cationized peptides. J Am Soc Mass Spectrom 16, 1305–1310 (2005). https://doi.org/10.1016/j.jasms.2005.01.028
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DOI: https://doi.org/10.1016/j.jasms.2005.01.028