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Activation and Dissociation of Deprotonated Peptides

1. A deprotonated parent peptide was isolated with


a series of radio frequency (rf) ejection pulses.
O O-
H2 H H2 H
C N H C N
H2N C NH H2N CH NH
2. This isolated, deprotonated peptide was H
activated by the application of rf excitation slightly O O- O HO

off resonance from the cyclotron frequency of the gly-gly-ile


O O
peptide ion.
NH2
H2 H
C N
H2N CH C O + O-
3. The deprotonated peptide oscillated with low
(<5 eV center of mass) translational energy. In the O
O
presence of a collision gas, the ion underwent Deprotonated C-terminus Amino Acid
multiple collisions—increasing the internal energy
of the ion over time until it underwent Scheme 1: Mechanism for the formation of a deprotonated C-terminus amino acid from
unimolecular dissociation. an isolated, deprotonated gly-gly-ile peptide.

Department of Chemistry
CHM 62200 1

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