Density functional theory studies on the oleic acid thermal oxidation into volatile compounds

Oleic acid oxidation is one of the main sources of food flavor compounds. Volatile profiling was investigated using thermal desorption cryo-trapping combined with gas chromatography–mass spectrometry to analyze the volatile composition of oleic acid oxidation. A total of 43 volatile compounds, including aldehydes (11), ketones (2), alcohols (5), furans (2), acids (8), ester (12) and alkane (3) were identified from oleic acid during heating. Then, density functional theory (DFT) was applied to analyze the oxidative mechanism of oleic acid during heating. A total of 30 reactions were obtained and grouped into the peroxide (ROOH), alkoxy radical (RO•), and peroxide radical (ROO•) pathways. The structures of intermediates, transition states (TS), and products in each reaction were also determined. Results show that the branch chemical reactions were the key reactions in different reaction pathway. Moreover, the reaction priority of the thermal oxidation reaction of oleic acid was the peroxide radical mechanism > the peroxide mechanism > the alkoxy radical mechanism.