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Updated: Jun 12, 2026

Synthesis and Mass Spectrometry Analysis of Oligo-peptoids
Published on: February 21, 2018
Gas-phase conformation-specific photofragmentation of proline-containing peptide ions
Tae-Young Kim1, Stephen J Valentine, David E Clemmer
1Department of Chemistry, Indiana University, Bloomington, Indiana, USA.
Abstract:
Singly-protonated proline-containing peptides with N-terminal arginine are photodissociated with vacuum ultraviolet (VUV) light in an ESI linear ion trap/orthogonal-TOF (LIT/o-TOF). When proline is the nth residue from the N-terminus, unusual b(n) + 2 and a(n) + 2 ions are observed. Their formation is explained by homolytic cleavage of the C(alpha)-C bond in conjunction with a rearrangement of electrons and an amide hydrogen. The latter is facilitated by a proline-stabilized gas-phase peptide conformation.
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