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.
Keywords: antioxidant; cut-off effect; interfacial phenomena; lipid hydroperoxides; lipid oxidation; mass transfer; micelles.