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Charge-Remote Fragmentation of Odd-Electron Peptide Ions

Journal Article · · Analytical Chemistry, 79(17):6607-6614
DOI:https://doi.org/10.1021/ac070777b· OSTI ID:915694
Comparison between gas-phase fragmentation of odd-electron M+• and [M-2H]-• ions of model peptides reported in this study demonstrates that charge-remote radical-driven fragmentation pathways play an important role in dissociation of odd-electron peptide ions. We found that charge-remote processes are responsible for a variety of side chain losses from the precursor ion and some backbone fragmentation. These fragmentation pathways most likely involve hydrogen abstraction from the β-carbon of the side chain by the radical site that initiates subsequent cleavages. The results reported in this work are generally relevant for understanding of fragmentation patterns of odd-electron peptide ions produced by different approaches including capture of low-energy electrons, electron detachment and electron transfer.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
915694
Report Number(s):
PNNL-SA-54810; 14395; KC0302020
Journal Information:
Analytical Chemistry, 79(17):6607-6614, Journal Name: Analytical Chemistry, 79(17):6607-6614 Journal Issue: 17 Vol. 79
Country of Publication:
United States
Language:
English

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