Factors Influencing the Antioxidant and Pro-Oxidant Activity of Polyphenols in Oil-in-Water Emulsions

The nonenzymatic oxidation of polyphenols bearing di- and trihydroxyphenol groups results in the generation of hydrogen peroxide (H2O2), a reactive oxygen species that can potentially compromise the oxidative stability of foods and beverages. An investigation of the factors that promote the oxidation of a model polyphenol, (-)-epigallocatechin-3-gallate (EGCG), was undertaken in a model lipid-based food system. Factors affecting oxidative stability, such as exogenous iron chelators (ethylenediaminetetraacetic acid; EDTA and 2,2-bipyridine; BPY) and pH (3 and 7) were evaluated in hexadecane and flaxseed oil-in-water (o/w) emulsions. At neutral pH, H2O2 levels were observed to rise rapidly in hexadecane emulsions except for EDTA-containing treatments. However, EDTA-containing samples showed the highest rate of EGCG oxidation, suggesting that H2O2 was rapidly reduced to hydroxyl radicals (HO center dot). Conversely, at pH 3, H2O2 concentrations were lower across all treatments. EDTA conferred the highest degree of EGCG stability, with no loss of the catechin over the course of the study. In order to assess whether or not the H2O2 production seen in oxidatively stable hexadecane emulsions translated to pro-oxidant activity in an oxidatively labile food lipid system, the effect of EGCG on the stability of flaxseed o/w emulsions was studied. EGCG displayed antioxidant activity at pH 7 throughout the study; however at pH 3, pro-oxidant activity was seen in EGCG-containing emulsions, with and without BPY. This study attempts to provide a mechanistic understanding of the conditions wherein polyphenols simultaneously exert pro-oxidant and antioxidant behavior in lipid dispersions.