ABSTRACT

Fatty acids with two or more double bonds, such as linoleic acid (LA; C18:2ω6) and arachidonic acid (AA; C20:4ω6), readily undergo autoxidation due to the ease by which a hydrogen atom can be abstracted from the molecule. Hydrogen abstraction occurs preferentially from the bis-allylic methylene and forms a carbon-centered radical that is delocalized over the pentadiene system. The fatty acid pentadienyl radical readily reacts with molecular oxygen to form a peroxyl radical. The peroxyl radical propagates the chain reaction by abstracting a bis-allylic hydrogen from an adjacent polyunsaturated fatty acid (PUFA). Thus, by cycling between carbon-centered and oxygen-centered radical forms, the initial radical generates multiple fatty acid

Introduction ..............................................................................................................25 Principal Reaction Pathways for Fatty Acid Peroxides ...........................................26