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 degrees 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 microM, an initial drop in dissolved oxygen (oxygen uptake rate >258 microM/min), followed by a slower linear oxygen uptake (oxygen uptake rate 4-6 microM/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 microM Fe2+/min). Fe3+ is reduced by peroxides to Fe2+ at a slow rate (0.25 microM Fe3+/min at 30 degrees 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 Fe (3+) 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.