title: Coordination sphere tuning of the electron transfer dissociation behavior of Cu(II)-peptide complexes.
abstract: In contrast to previous electron capture dissociation (ECD) studies, we find that electron transfer dissociation (ETD) of Cu(II)-peptide complexes can generate c- and z-type product ions when the peptide has a sufficient number of strongly coordinating residues. Double-resonance experiments, ion-molecule reactions, and collision-induced dissociation (CID) prove that the c and z product ions are formed via typical radical pathways without the associated reduction of Cu(II), despite the high second ionization energy of Cu. A positive correlation between the number of Cu(II) binding groups in the peptide sequence and the extent of c and z ion formation was also observed. This trend is rationalized by considering that the recombination energy of Cu(II) can be lowered by strong binding ligands to an extent that enables electron transfer to non-Cu sites (e.g., protonation sites) to compete with Cu(II) reduction, thereby generating c/z ions in a manner similar to that observed for protonated (i.e., nonmetalated) peptides.
authors.affiliation: Department of Chemistry, University of Massachusetts, LGRT 701, 10 N. Pleasant St., Amherst, MA 01003, USA.
authors.forename: Jia
authors.initials: J
authors.lastname: Dong
authors.forename: Richard W
authors.initials: RW
authors.lastname: Vachet
mesh_terms: D000595:Amino Acid Sequence; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D008969:Molecular Sequence Data; D010455:Peptides / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D056831:Coordination Complexes; D010455:Peptides; D003300:Copper