The effect of heating on the formation of 4-hydroxy-2-hexenal and 4-hydroxy-2-nonenal in unsaturated vegetable oils: Evaluation of oxidation indicators.

The formation of 4-hydroxy-2-hexenal (HHE) and 4-hydroxy-2-nonenal (HNE) in vegetable oils and model oil systems were quantitatively assessed by RP-HPLC. Regardless of heating temperature, HHE was only detected in rapeseed and linseed oil, while HNE was detected in all tested oils. Intrinsic tocopherols suppressed HHE/HNE formation, but with similar inhibition rates (10.49-16.04%). Linear correlations were observed between HHE/HNE contents and corresponding n-3/6 fatty acid content in oils (R² = 0.989/0.971). Model oil system revealed that HHE/HNE formation was closely related to methyl linolenate (MLN) and methyl linoleate (ML) contents. Low levels of ML (<0.5%) and MLN (<1.0%) did not lead to HHE/HNE formation. Therefore, HHE/HNE was classified as the characteristic aldehydes of n-3 and n-6 type oils, respectively. Heat map evaluation and regression analysis indicated HHE could predict the n-3 type oils oxidation, while HNE was a good indicator to estimate the oxidative deterioration of n-6 and n-9 type oils.