Impact of hydrogen bonding on the susceptibility of peptides to oxidation

Bun Chan*, Damian Moran, Christopher J. Easton, Leo Radom

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)


The tendency of peptides to be oxidized is intimately connected with their function and even their ability to exist in an oxidative environment. Here we report high-level theoretical studies that show that hydrogen bonding can alter the susceptibility of peptides to oxidation, with complexation to a hydrogen-bond acceptor facilitating oxidation, and vice versa, impacting the feasibility of a diverse range of biological processes. It can even provide an energetically viable mechanistic alternative to direct hydrogen-atom abstraction. We find that hydrogen bonding to representative reactive groups leads to a broad (≈400 kJ mol−1) spectrum of ionization energies in the case of model amide, thiol and phenol systems. While some of the oxidative processes at the extreme ends of the spectrum are energetically prohibitive, subtle environmental and solvent effects could potentially mitigate the situation, leading to a balance between hydrogen bonding and oxidative susceptibility.

Original languageEnglish
Pages (from-to)1485-1489
Number of pages5
JournalChemistry - An Asian Journal
Issue number13
Publication statusPublished - 4 Jul 2017
Externally publishedYes


  • amino acids
  • hydrogen bonding
  • ionization energies
  • oxidation
  • peptides
  • theoretical calculations


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