Abstract
In lipid dispersions, the ability of reactants to move from one lipid particle to another is an important, yet often ignored, determinant of lipid oxidation and its inhibition by antioxidants. This review describes three putative interparticle transfer mechanisms for oxidants and antioxidants: (a) diffusion, (b) collision-exchange-separation, and (c) micelle-assisted transfer. Mechanism a involves the diffusion of molecules from one particle to another through the intervening aqueous phase. Mechanism b involves the transfer of molecules from one particle to another when the particles collide with each other. Mechanism c involves the solubilization of molecules in micelles within the aqueous phase and then their transfer between particles. During lipid oxidation, the accumulation of surface-active lipid hydroperoxides (LOOHs) beyond their critical micelle concentration may shift their mass transport from the collision-exchange-separation pathway (slow transfer) to the micelle-assisted mechanism (fast transfer), which may account for the transition from the initiation to the propagation phase. Similarly, the cut-off effect governing antioxidant activity in lipid dispersions may be due to the fact that above a certain hydrophobicity, the transfer mechanism for antioxidants changes from diffusion to collision-exchange-separation. This hypothesis provides a simple model to rationalize the design and formulation of antioxidants and dispersed lipids.
Highlights
More than a century ago, researchers first noted that lipids oxidize by a free radical mechanism, and in the 1940s, they identified the three stages involved in the chain reaction: initiation, propagation, and termination (Schaich 2013)
This point is of paramount importance because if a lag phase occurs in antioxidant-free emulsions or membrane systems, it implies that the antioxidant depletion does not trigger by itself the increase of LOOHs
This review paves the way for the consideration of mass transfer phenomena as being highly influential in lipid oxidation and its inhibition by antioxidants in lipid dispersions
Summary
Antioxidant, interfacial phenomena, mass transfer, lipid hydroperoxides, micelles, cut-off effect
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