Average and maximum charge states of arginine-containing dendrimer-like peptide ions formed by electrospray ionization

Abstract

The maximum and average charge states formed by electrospray ionization of dendrimer-like multiple antigenic peptides (MAPs) which differ in structure only in the presence of an arginine residue at the N-termini of their four peptide chains have been investigated. Stepwise addition of arginine residues leads to increased charging. It has been found that the average charge state is linearly correlated to the number of arginine residues which allows the conclusion that the four peptide chains are effectively independent. The average charge state zav is shifted with each added arginine residue by roughly 0.3 units towards lower m/z ratios. Modification of the alpha-amino groups by acetylation reduces zav as compared with the corresponding non-modified model peptides. This suggests that the N-terminal arginineis to some extent protonatedon both its alpha-amino group and its side-chain guanidino group. The Coulomb repulsion is presumably reduced through intramolecular charge solvation in the N-terminal part of the peptide chains.