Caffeic Acid as Antioxidant in Fish Muscle: Mechanism of Synergism with Endogenous Ascorbic Acid and α-Tocopherol

In an emulsion of corn oil in water with the addition of caffeic acid (Caf-OH) and alpha-tocopherol (alpha-TOH), Caf-OH was found to be very active in delaying lipid oxidation without affecting significantly the kinetics for a-TOH degradation. In contrast, Caf-OH addition to fish muscle retarded both the degradation of endogenous alpha-TOH and the propagation of lipid oxidation, measured by peroxide value (PV) and thiobarbituric acid reactive substances (TBARS), with increasing effect with increasing Caf-OH addition (55.5-555.1 mu mol/kg). Electron spin resonance (ESR) spectroscopy confirmed a higher capacity of Caf-OH to regenerate alpha-TOH via reduction of the alpha-tocopheroxyl radical compared to other cinnamic acid derivatives (o-coumaric, ferulic, and chlorogenic acids). Degradation of endogenous ascorbate (AscH(-)) was accelerated at higher concentration of Caf-OH in fish tissue, suggesting a role of AscH- in the regeneration of Caf-OH. These results indicate that the antioxidant mechanism of Caf-OH implies the protection of endogenous alpha-TOH localized in tissue membranes where lipid oxidation is initiated and, at the same time, Caf-OH regeneration by the endogenous AscH-. These combined effects result in a stronger antioxidant protection against lipid oxidation by favoring, as a final point, the protection of alpha-TOH, which is suggested as the last defense of fish muscle against lipid oxidation.