Thermally induced formation of conjugated isomers of linoleic acid

Abstract

Chemical pathways responsible of the conjugation of linoleic acid during heat treatments such as refining (deodorization), frying or cooking processes have been investigated. For this purpose, methyl linoleate was submitted to oxidative and non-oxidative thermal conditions. The resulting degradation products were mainly composed of geometrical and conjugated fatty acid isomers. Oxidative conditions were obtained using tert-butyl hydroperoxide under inert atmosphere, and air. The obtained results from both thermal oxidative conditions were compared to non-oxidative thermal treatment. Higher levels of conjugated linoleic acid were found when linoleate was heated under oxidative conditions. Two distinct mechanisms responsible for the formation of CLA isomers are proposed and discussed. Evidence of formation of 9,11-C18:2 and 10,12-C18:2 acids from 9,12-C18:2 by a free-radical chain reaction is provided. The first step consists in the formation of a free radical by abstraction of an active bis-allylic hydrogen. By delocalization of the initial free radical, two allylic free radicals were stabilized and converted into the corresponding CLA isomers via the abstraction of a hydrogen radical from other linoleic acid or oxygenated species. Kinetic observations confirmed the significance of the bimolecular mechanism. Moreover, the proposed mechanism is supported by several pieces of information from the literature on peroxidation of linoleic acid. Under pure thermal conditions and/or for diluted samples, a second pathway to the formation of CLA from heat-treated linoleic acid is proposed via an intramolecular rearrangement of the pentadienyl structure. This thermal [1,3]-sigmatropic rearrangement results in a mixture of 9,11 and 10,12 CLA isomers. The formed cis/trans CLA isomers were readily rearranged by a [1,5]-sigmatropic shift to yield trans-8,cis-10 and cis-11,trans-13 CLA isomers, respectively.