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J Am Soc Mass Spectrom. 2005 Jun;16(6):880-2. Epub 2005 Apr 14.

Electron transfer dissociation of peptide anions.

Author information

1
Department of Chemistry, University of Virginia, McCormick Road, Charlottesville, VA 22908, USA. jcoon@virginia.edu

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.

PMID:
15907703
DOI:
10.1016/j.jasms.2005.01.015
[Indexed for MEDLINE]
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