Targeting Antioxidants to Interfaces: Control of the Oxidative Stability of Lipid-Based Emulsions.

The oxidation of lipid-based emulsions and nanoemulsions strongly affects their overall quality and safety. Moreover, introduction of oxidatively unstable emulsions into biological systems either as an energy source in parenteral nutrition or as delivery systems of bioactives may promote oxidation "in situ" leading to the overproduction of reactive oxygen species, initiating new harmful oxidative reactions and increasing the oxidative damage. Addition of antioxidants, AOs, may help to prevent the oxidative degradation of unsaturated lipids. Nevertheless, prediction of the optimal antioxidant or set of antioxidants and their efficiency is still far from being completely understood because the site of reaction is often uncertain and because the effective concentrations of reactants in the different regions of the emulsion have been frequently overlooked. Furthermore, the absence of quantitative relationships between the hydrophobicity of the antioxidants and their partitioning among the oil, water, and interfacial regions hampers their optimal use. Here we investigated the effects of gallic acid and some of its alkyl derivatives on the oxidative stability of soybean oil-in-water emulsions and determined their effective concentrations in the different regions of the emulsion (aqueous, oil, and interface). The results provide physical evidence for the crucial role played by the interfacial region in the reaction between antioxidants and lipid radicals: a direct relationship between interfacial concentrations and the oxidative stability could be established. The results indicate that AOs accumulate in the interfacial region, where the effective concentration is 20-180 times higher than the stoichiometric concentrations. Control of the hydrophobicity of the AOs and of the surfactant concentration allows control of interfacial concentrations: the lower the concentration of surfactant employed, the higher the effective interfacial concentration.