title: Electron transfer dissociation of peptide anions.
abstract: Ion/ion reactions of multiply deprotonated peptide anions with xenon radical cations result in electron abstraction to generate charge-reduced peptide anions containing a free-radical site. Peptide backbone cleavage then occurs by hydrogen radical abstraction from a backbone amide N to facilitate cleavage of the adjacent C-C bond, thereby producing a- and x-type product ions. Introduction of free-radical sites to multiply charged peptides allows access to new fragmentation pathways that are otherwise too costly (e.g., lowers activation energies). Further, ion/ion chemistry, namely electron transfer reactions, presents a rapid and efficient means of generating odd-electron multiply charged peptides; these reactions can be used for studying gas-phase chemistries and for peptide sequence analysis.
authors.affiliation: Department of Chemistry, University of Virginia, McCormick Road, Charlottesville, VA 22908, USA. jcoon@virginia.edu
authors.forename: Joshua J
authors.initials: JJ
authors.lastname: Coon
authors.forename: Jeffrey
authors.initials: J
authors.lastname: Shabanowitz
authors.forename: Donald F
authors.initials: DF
authors.lastname: Hunt
authors.forename: John E P
authors.initials: JE
authors.lastname: Syka
mesh_terms: D000595:Amino Acid Sequence; D000838:Anions / Q000737:chemistry; D004579:Electron Transport; D008958:Models, Molecular; D008969:Molecular Sequence Data; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry*; D055672:Static Electricity
chemical_list: D000838:Anions; D010455:Peptides