The free radical oxidation of lipids is associated with many degenerative conditions in humans.  Lipid peroxidation is observed in circumstances as diverse as viral infections and neurodegenerative disease but the fundamental chemical transformation, a free radical chain carried by intermediate peroxyls, is common to all of these pathologies.  The rate constants for the slow propagation step of peroxidation of several lipids have been determined by a radical clock method and 7-dehydrocholesterol, an intermediate in the biosynthesis of cholesterol, has been found to be the most oxidizable lipid known. Elevated levels of 7-dehydrocholesterol are associated with a neurodevelopmental condition known as Smith-Lemli-Opitz syndrome and evidence is presented that link lipid peroxidation of 7-dehydrocholesterol to this disorder.   The peroxidation of deuterated natural lipids show primary isotope effects that are larger than expected, indicating that tunneling may be associated with H-atom transfer to peroxyl radicals.

Award Address  (James Flack Norris Award in Physical Organic Chemistry sponsored by the ACS Northeastern Section). Mechanisms of free radical oxidation reactions of lipids: Kinetics, products, and human pathologies

245th National Meeting (2013)

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