Comparison between the gas-phase fragmentation of odd-electron M
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, [M + H]
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, and [M - 2H]
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ions of modelpeptides suggests that charge-remote radical-driven fragmentation pathways play an important role in the dissociation of odd-electron peptide ions. We have found thatcharge-remote processes are responsible for a variety ofside-chain losses from the precursor ion and somebackbone fragmentation. These fragmentation pathwaysmost likely involve hydrogen abstraction by the radical sitethat initiates subsequent cleavages. These findings aregenerally relevant to our understanding of the fragmentation patterns of odd-electron peptide ions producedthrough various approaches including the capture of low-energy electrons, electron detachment, and electron transfer.