Fragmentation of an alkali metal-attached peptide probed by collision-induced dissociation Fourier transform mass spectrometry and computational methodology

by Tomlinson, Medha J.; Scott, Jill R.; Wilkins, Charles L.; Wright, Jeffery B.; White, William E.

Collision-induced dissociation of metal-cationized N-CBZ-Gly-Pro-Gly-Pro-Ala was studied by Fourier transform mass spectrometry. Lithium-, sodium-, potassium- and rubidium-cationized peptide species were generated by matrix-assisted laser desorption/ionization (MALDI) using 2,5-dihdroxybenzoic acid as matrix, together with appropriate metal salts, The experimental mass spectrometric results were interpreted with the aid of Monte Carlo conformational searches using the Amber* force field, together with ab initio molecular orbital calculations with Gaussian-94 for the singly lithium- and potassium-cationized peptides. It is concluded that metal coordination plays a key role in guiding thc gas-phase fragmentation of the cationized peptide. In contrast to lithium and sodium, potassium and rubidium apparently do not coordinate to the C-terminal carbonyl, When the peptide is cationized with the two smaller alkali metals, losses corresponding to alanine and CBZ are observed, while the coordination of potassium and rubidium results in only CBZ loss upon dissociation. Copyright (C) 1999 John Wiley & Sons, Ltd.

Journal
Journal of Mass Spectrometry
Volume
34
Issue
9
Year
1999
Start Page
958
ISBN/ISSN
1096-9888; 1076-5174
DOI
10.1002/(SICI)1096-9888(199909)34:9<958::AID-JMS858>3.0.CO;2-A