The Role of Iron in Peroxidation of Polyunsaturated Fatty Acids in Liposomes

This work investigated iron-catalyzed lipid oxidation in marine phospholipid liposomes. Oxygen consumption was used as a method to study lipid oxidation at pH 5.5 and 30 °C. The relationship between consumed oxygen and amount of peroxides (PV) and thiobarbituric reactive substances (TBARS) formed showed that both Fe2+ and Fe3+ catalyzed lipid oxidation. When Fe2+ was added to liposomes at a concentration of approximately 10 µM, an initial drop in dissolved oxygen (oxygen uptake rate >258 µM/min), followed by a slower linear oxygen uptake (oxygen uptake rate 4–6 µM/min), was observed. Addition of Fe3+ induced only the linear oxygen uptake. The initial fast drop in dissolved oxygen was due to oxidation of Fe2+ to Fe3+ by preexisting lipid peroxides (rate 79 µM Fe2+/min). Fe3+ is reduced by peroxides to Fe2+ at a slow rate (0.25 µM Fe3+/min at 30 °C) in a pseudo-first-order reaction. The redox cycling between Fe2+ and Fe3+ leads to an equilibrium between Fe2+ and Fe3+ resulting in a linear oxygen uptake. During the linear oxygen uptake, the interaction of Fe3+ with lipid peroxide is the rate-limiting factor. Both alkoxy and peroxy radicals are formed by breakdown of peroxides by Fe2+ and Fe3+. These radicals react with fatty acids giving lipid radicals reacting with oxygen.