Lipid oxidation in emulsions is influenced by the ability of transition metals to associate with emulsion droplets. The oxidative stability of 5% salmon oil-in-water emulsion was influenced by surfactant type, with oxidation rates being greatest in emulsions stabilized by anionic sodium dodecyl sulfate (SDS) followed by nonionic Tween 20 and cationic dodecyltrimethylammonium bromide (DTAB). EDTA inhibited lipid oxidation in all the emulsions, and apo-transferrin inhibited oxidation in the Tween 20-stabilized emulsions at pH 7.0, suggesting that continuous-phase iron was an active prooxidant. Iron associated with Tween-20 stabilized hexadecane emulsion droplets could be partitioned into the continuous phase by lowering the pH to =4.0 or by the presence of EDTA, which could help explain why low pH and EDTA decrease lipid oxidation rates. These data suggest that iron is an important lipid oxidation catalyst in salmon oil emulsions, and factors that increase iron-emulsion droplet interactions will increase oxidation rates.
Free radicals arising from lipid peroxides accelerate the oxidative deterioration of foods. To elucidate how lipid peroxides impact oxidative reactions in food emulsions, the stability of cumene hydroperoxide was studied in hexadecane or trilaurin emulsions stabilized by anionic (sodium dodecyl sulfate; SDS), nonionic (Tween 20), and cationic (dodecyltrimethylammonium bromide; DTAB) surfactants. Fe(2+) rapidly (within 10 min) decomposed between 10 and 31% of the cumene hydroperoxide in Tween 20- and DTAB-stabilized emulsions at pH 3.0 and 7.0 and in the SDS-stabilized emulsion at pH 7.0 with no further decomposition of peroxides occurring for up to 3 h. In SDS-stabilized emulsions at pH 3.0, Fe(2+) decreased peroxides by 90% after 3 h. Decomposition of peroxides in the absence of added iron and by Fe(3+) was observed only in SDS-stabilized emulsions at pH 3.0. These results suggest that peroxide decomposition by iron redox cycling occurs when iron emulsion droplet interactions are high.
Peroxides are an important factor in oxidative reactions in foods because their decomposition can result in formation of highly reactive free radicals. Emulsifiers such as the Brijs, Tweens, and lecithin were found to contain 4-35 micromol of peroxides/g of surfactant. Peroxide concentrations in Tween 20 micelles increased in the presence of low iron concentrations but decreased when iron concentrations were high, suggesting that iron was capable of promoting both peroxide formation and decomposition. Oxidation of alpha-tocopherol was observed in micelles high in peroxides (Tween 20) but not in micelles where peroxide concentrations were low (Brij). Transition metals accelerated the oxidation of alpha-tocopherol in Tween 20 micelles, whereas EDTA stabilized alpha-tocopherol in the presence of added Fe(2+). These results suggest that surfactant peroxides could decrease the oxidative stability of food emulsions by acting as a source of free radicals, especially in the presence of transition metals.
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