Analysis of the kinetics of lipid peroxidation in terms of characteristic time-points

• Inhibited peroxidation of lipids is followed by a stage of relatively fast oxidation.
• TMI-induced peroxidation is accelerated by reaction products – hydroperoxides.
• The resultant complex kinetics is characterized by a limited number of unambiguous parameters.
• The whole kinetic profiles are described on the basis of mechanistic considerations.
• The meaning of characteristic time-points is given in terms of rate constants and concentrations.

Measuring peroxidation of aggregated lipids in model systems (liposomes, micelles, emulsions or microemulsions) as well as in samples of biological origin ex vivo (isolated lipoproteins, blood sera or plasma) is widely used in medical and biological investigations, to evaluate the oxidative stress, antioxidants’ efficiency and lipid oxidizability in different pathophysiological states. To avoid possible artifacts, such investigations must be based on the time course of peroxidation (i.e. on kinetic studies). To be able to compare complex kinetic profiles, it is important to characterize them in terms of mechanistically meaningful and experimentally unequivocal parameters.In this review, we characterize the typically observed continuous kinetic profiles in terms of a limited number of characteristic time-points (both commonly used and additional time-points and their combinations) that can be derived from experimental time-dependencies. The meaning of each of the experimentally observed characteristic parameters is presented in terms of rate constants and concentrations, derived on the basis of mechanistic considerations. Theoretical expressions for these characteristic parameters are based on a model that includes both the inhibited peroxidation and the uninhibited peroxidation occurring after consumption of the antioxidant(s). Comparison between theoretically predicted dependencies and experimental data support our treatment considered with special emphasis on transition metals-induced peroxidation of lipoproteins.