Evidence that Criegee intermediates drive autoxidation in unsaturated lipids
- 2 March 2020
- journal article
- research article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences of the United States of America
- Vol. 117 (9), 4486-4490
- https://doi.org/10.1073/pnas.1920765117
Abstract
Autoxidation is an autocatalytic free-radical chain reaction responsible for the oxidative destruction of organic molecules in biological cells, foods, plastics, petrochemicals, fuels, and the environment. In cellular membranes, lipid autoxidation (peroxidation) is linked with oxidative stress, age-related diseases, and cancers. The established mechanism of autoxidation proceeds via H-atom abstraction through a cyclic network of peroxy-hydroperoxide-mediated free-radical chain reactions. For a series of model unsaturated lipids, we present evidence for an autoxidation mechanism, initiated by hydroxyl radical (OH) addition to C=C bonds and propagated by chain reactions involving Criegee intermediates (CIs). This mechanism leads to unexpectedly rapid autoxidation even in the presence of water, implying that as reactive intermediates, CI could play a much more prominent role in chemistries beyond the atmosphere.Keywords
Funding Information
- DOE | SC | Basic Energy Sciences (DE-AC02-05CH11231)
This publication has 37 references indexed in Scilit:
- The direct observation of secondary radical chain chemistry in the heterogeneous reaction of chlorine atoms with submicron squalane dropletsPhysical Chemistry Chemical Physics, 2011
- Quantifying the reactive uptake of OH by organic aerosols in a continuous flow stirred tank reactorPhysical Chemistry Chemical Physics, 2009
- Targeting cancer cells by ROS-mediated mechanisms: a radical therapeutic approach?Nature Reviews Drug Discovery, 2009
- The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosolsAtmospheric Chemistry and Physics, 2009
- The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosolsPublished by Copernicus GmbH ,2009
- Neurodegenerative diseases and oxidative stressNature Reviews Drug Discovery, 2004
- Crystallization of designed protein variantsMethods, 1990
- Mechanism of OzonolysisAngewandte Chemie-International Edition, 1975
- Kinetics of olefin oxidationQuarterly Reviews, Chemical Society, 1949