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Theoretical modeling of hydroxyl-radical-induced lipid peroxidation reactions
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Tejero, Ismael (author)
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Gonzalez-Lafont, Angels (author)
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Lluch, José M. (author)
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- Eriksson, Leif A. (author)
- Örebro universitet,Institutionen för naturvetenskap,Biophysical Chemistry
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(creator_code:org_t)
- 2007-05-02
- 2007
- English.
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In: Journal of Physical Chemistry B. - : American Chemical Society. - 1520-6106 .- 1520-5207. ; 111:20, s. 5684-5693
- Related links:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
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- 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 C11 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.
Subject headings
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
Keyword
- Hydroxyl Radical
- Lipid Peroxidation
- Lipid Models
- Molecular Structure
- Thermodynamics
- Computational Chemistry
- Theoretical chemistry
- Teoretisk kemi
- NATURAL SCIENCES
- NATURVETENSKAP
- Chemistry
- Kemi
- Fysikalisk kemi
- Physical Chemistry
- Chemistry
- Kemi
Publication and Content Type
- ref (subject category)
- art (subject category)
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