Peptide derivatization as a strategy to form fixed-charge peptide radicals

Abstract

As a means of generating fixed-charge peptide radicals in the gas phase we have examined the collision-induced dissociation (CID) chemistry of ternary [CuII(terpy)(TMPP-M)]2+ complexes, where terpy = 2,2′:6′2″-terpyridine and TMPP-M represents a peptide (M) modified by conversion of the N-terminal amine to a [tris(2,4,6- trimethoxyphenyl)phosphonium]acetamide (TMPP-) fixed-charge derivative. The following modified peptides were examined: oligoglycines, (Gly)n (n = 1-5), alanylglycine, glycylalanine, dialanine, trialanine and leucine-enkephaline (YGGFL). The [CuII (terpy)(TMPP-M)]2+ complexes are readily formed upon electrospray ionization (ESI) of a mixture of derivatized peptide and [CuII(t..