Abstract
Selecting effective antioxidants is challenging since their efficiency in inhibiting lipid oxidation depends on the rate constants of the chemical reactions involved and their concentration at the reaction site, i.e., at the interfacial region. Accumulation of antioxidants at the interface of emulsions is key to modulate their efficiency in inhibiting lipid oxidation but its control was not well understood, especially in emulsions. It can be optimized by modifying the physicochemical properties of antioxidants or the environmental conditions. In this work, we analyze the effects of surfactant concentration, droplet size, and oil to water ratio on the effective interfacial concentration of a set of chlorogenic acid (CGA) esters in fish oil-in-water (O/W) emulsions and nanoemulsions and on their antioxidant efficiency. A well-established pseudophase kinetic model is used to determine in the intact emulsified systems the effective concentrations of the antioxidants (AOs). The relative oxidative stability of the emulsions is assessed by monitoring the formation of primary oxidation products with time. Results show that the concentration of all AOs at the interfacial region is much higher (20–90 fold) than the stoichiometric one but is much lower than those of other phenolipid series such as caffeic or hydroxytyrosol derivatives. The main parameter controlling the interfacial concentration of antioxidants is the surfactant volume fraction, ΦI, followed by the O/W ratio. Changes in the droplet sizes (emulsions and nanoemulsions) have no influence on the interfacial concentrations. Despite the high radical scavenging capacity of CGA derivatives and their being concentrated at the interfacial region, the investigated AOs do not show a significant effect in inhibiting lipid oxidation in contrast with what is observed using other series of homologous antioxidants with similar reactivity. Results are tentatively interpreted in terms of the relatively low interfacial concentrations of the antioxidants, which may not be high enough to make the rate of the inhibition reaction faster than the rate of radical propagation.
Highlights
Polyunsaturated fatty acids (PUFAs) are an essential part of parenteral nutrition, which is considered a lifesaving therapy [1,2]
Results confirm that the fraction of emulsifier has a significant influence on the fraction of antioxidant found in each phase: the higher ΦI, the greater the percentage of antioxidant present in the interfacial region
The results in this work highlight the great complexity of the oxidative phenomena and its inhibition by antioxidants (AOs) in emulsified systems, addressing some of the points that need to be considered in future studies to fully understand all the factors that contribute for the oxidative stability of emulsified systems
Summary
Polyunsaturated fatty acids (PUFAs) are an essential part of parenteral nutrition, which is considered a lifesaving therapy [1,2]. There was great interest in using fish oils in food products mainly becaus of the high content of long chain omega-3 PUFAs present in their triacylglycerols, espe cially docosahexaenoic acid (DHA, C22: 6, ⍵-3) and eicosapentaenoic acid ⍵-3) [4,5,6] These omega-3 PUFAs showed clear health benefits to consumers [7] and, as consequence, incorporation of fish oil into has increased, above all, inofcountrie recent years, there was great interest in using fish foods oils in food products mainly because the highthere content long chainofomega-3 in their triacylglycerols, especially where is of a shortage fish andPUFAs foodspresent enriched in omega-3. Poration decreases the oxidative stability of foods because EPA and DHA are quickly ox These omega-3 showed clear health benefits of to consumers and, as a consequence, idized. Eicosapentaenoic acid (EPA, C20: 5, ř-3) [4,5,6].
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