Electron transfer dissociation of peptide anions |
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Authors: | Email author" target="_blank">Joshua?J?CoonEmail author Jeffrey?Shabanowitz Donald?F?Hunt John?E?P?Syka |
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Institution: | (1) Center for Intelligent Chemical Instrumentation, Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701–2979, USA; |
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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. |
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Keywords: | |
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