Thinking outside the classical chain reaction box of lipid oxidation

For the past few decades, research on lipid oxidation mechanisms has been rather stagnant due to a pervasive attitude that reactions of lipid oxidation were well understood, so only tailoring applications of basic knowledge to stabilize individual systems was needed. This simplistic approach worked during the low fat/no fat era because there was little lipid substrate to oxidize. However, with current reformulation of foods with polyunsaturated fatty acids for health, preventing oxidation of these essential fatty acids presents major challenges that cannot always be solved with traditional thinking. Because critical gaps in our understanding prevent moving forward with improved processing, formulations, and packaging to provide high-PUFA lipid foods that remain shelf-stable beyond a few months, details about oxidation mechanisms that were previously considered irrelevant have now become critically important. Considered here are alternate reaction pathways that compete with classical hydrogen abstraction and must be integrated into the overall free radical chain to more accurately account for kinetics and products of lipid oxidation.