Reactions between peroxidizing lipids and histidyl residue analogues: enhancement of lipid oxidation and browning by 4-methylimidazole.

ABSTRACT

As a part of our study on the interactions between peroxidizing lipids and the histidyl imidazole side-chain in simple, low-moisture model systems, 4-methylimidazole (4MI) was reacted with methyl linoleate (ML). This analogue was chosen to avoid interference from other functional groups in histidine (free base) or in proteins. Changes in the concentrations of lipid hydroperoxides, carbonyls, 4MI, and brown pigments were followed over a period of 24 days. The results indicate that 4MI exhibits significant prooxidative activity by reducing the induction period as well as by enhancing the formation of brown pigments. These effects are more pronounced at high 4MI/MI molar ratios and under basic pH's. Upon interactions with peroxidizing ML, as much as 44% of initially present 4MI was destroyed by the sixth day of incubation.