Mechanism of formation of trans fatty acids under heating conditions in triolein.

To elucidate the relationship between heat-induced cis/trans isomerization and reaction temperature and energy in unsaturated lipids, we investigated the molecular mechanism of the heat-induced cis/trans isomerization of 18:1 isomers. Triolein (18:1,9c) was heated at two range temperatures (130, 160, 190, 220 °C and 135, 140, 145, 150, 155 °C) and analyzed by the gas chromatography (GC) method. When the heating temperature increased to 150 °C, the amount of trans 18:1n-9 changed from 0.0897 mg/g oil (1 h) to 0.1700 mg/g oil (3 h). This study shows that the cis to trans isomerization may occur at 150 °C. The formation of fatty acid isomers followed a proton transfer route. All key geometries, transition states, intermediates, and bond dissociation energies (BDE) were optimized at the B3LYP/6-31G* level for the density functional theory (DFT). The zero-point energy corrections of the isomers were carried out using calculations at the B3LYP/6-311++G** level. The calculated energy difference between the cis and trans oleic acid was equal to 7.6 kJ/mol, and the energy barriers of the transition from cis 18:1n-9 to trans 18:1n-9 were 294.5 kJ/mol. The intrinsic reaction coordinates (IRCs) were obtained to be used as an expression of the reaction route and to analyze the transition states and intermediates. The study results suggest that the heating temperature should be kept under 150 °C, to avoid the risk of trans fatty acid (TFA) intake in daily food.