Explaining the antioxidant activity of some common non-phenolic components of essential oils

Limonene, linalool and citral are common non-phenolic terpenoid components of essential oils, with attributed controversial antioxidant properties. The kinetics of their antioxidant activity was investigated using the inhibited autoxidation of a standard model substrate. Results indicate that antioxidant behavior of limonene, linalool and citral occurs by co-oxidation with the substrate, due to very fast self-termination and cross-termination of the oxidative chain. Rate constants k(p) and 2k(t), (M-1 s(-1)) at 30 degrees C were 4.5 and 3.5 x 10(6) for limonene, 2.2 and 9.0 x 10(5) for linalool and 39 and 1.0 x 10(8) for citral. Behavior is bimodal antioxidant/pro-oxidant depending on the concentration. Calculations at the M05/6-311+g(2df, 2p) level indicate that citral reacts selectively at the aldehyde C-H having activation enthalpy and energy respectively lower by 1.3 and 1.8 kcal/mol compared to the most activated allyl position. Their termination-enhancing antioxidant chemistry might be relevant in food preservation and could be exploited under appropriate settings. (C) 2017 Published by Elsevier Ltd.