Molecular mechanism of saturated aldehyde oxidation: A DFT insight into volatiles forming from decanal thermal oxidation.

Decanal is one of the main products of lipid oxidation. It has been shown that decanal can oxidize to form volatiles with shorter carbon chains during heating, but the mechanism is still unclear. In this study, volatile compounds formed in the decanal thermal oxidation were verified using thermal-desorption cryo-trapping combined with GC–MS. A total of 32 volatile compounds were identified. The oxidation mechanism of decanal was studied by applying density functional theory. Results revealed that the carbonyl carbon atom was the thermal oxidation site of decanal and two pathways of peroxide oxidation were determined: the ortho‑carbon and the meta‑carbon oxidation. The ortho‑carbon oxidation pathway is superior to the occurrence of the meta‑carbon oxidation pathway. The oxidative mechanism of decanal was finally summarized as the peroxide oxidation based on radical attack on the carbonyl carbon, which would provide a theoretical basis for exploring the oxidation mechanism of other saturated aldehydes. [Display omitted] • Carbonyl carbon atom was the thermal oxidation site of decanal. • Oxidative cleavage of decanal was caused by peroxides formed by free radical attack. • Ortho‑carbon and meta‑carbon oxidation pathways were elaborated. • Priority order was ortho‑carbon oxidation pathway > meta‑carbon oxidation pathway. [ABSTRACT FROM AUTHOR]