Theoretical modeling of hydroxyl-radical-induced lipid peroxidation reactions

Ismael Tejero, Ángels González-Lafont, José M. Lluch, Leif A. Eriksson

Research output: Contribution to journalArticleResearchpeer-review

38 Citations (Scopus)


The OH-radical-induced mechanism of lipid peroxidation, involving hydrogen abstraction followed by O2 addition, is explored using the kinetically corrected hybrid density functional MPWB1K in conjunction with the MG3S basis set and a polarized continuum model to mimic the membrane interior. Using a small nonadiene model of linoleic acid, it is found that hydrogen abstraction preferentially occurs at the mono-allylic methylene groups at the ends of the conjugated segment rather than at the central bis-allylic carbon, in disagreement with experimental data. Using a full linoleic acid, however, abstraction is correctly predicted to occur at the central carbon, giving a pentadienyl radical. The Gibbs free energy for abstraction at the central C 11 is ∼8 kcal/mol, compared to 9 kcal/mol at the end points (giving an allyl radical). Subsequent oxygen addition will occur at one of the terminal atoms of the pentadienyl radical fragment, giving a localized peroxy radical and a conjugated butadiene fragment, but is associated with rather high free energy barriers and low exergonicity at the CPCM-MPWB1K/MG3S level. The ZPE-corrected potential energy surfaces obtained without solvent effects, on the other hand, display considerably lower barriers and more exergonic reactions. © 2007 American Chemical Society.
Original languageEnglish
Pages (from-to)5684-5693
JournalJournal of Physical Chemistry B
Issue number20
Publication statusPublished - 24 May 2007


Dive into the research topics of 'Theoretical modeling of hydroxyl-radical-induced lipid peroxidation reactions'. Together they form a unique fingerprint.

Cite this