Determination of thermal oxidation and oxidation products of β-carotene in corn oil triacylglycerols

A reversed phase HPLC-DAD coupled to APCI-MS method is reported for the determination of the degradation of β-carotene and characterization of the oxidation products in corn oil. Corn oil containing β-carotene was oxidized in the Rancimat at 110 °C from 1 to 14 h. A significant degradation of β-carotene was observed in corn oil during accelerated thermal oxidation. A total of eight different oxidized products of β-carotene were identified, which includes 8′-apo-β-carotenal, 6′-apo-β-carotenal, 5,6-epoxy-8′-apo-β-carotenal, β-carotene-2,2′-dione, 13-Z-5,6,5′,6′-diepoxy-β-carotene, all-E-5,8-epoxy-β-carotene, all-E-5,6-epoxy-β-carotene, and 15-Z-5,6-epoxy-β-carotene. Corn oil triacylglycerols (TAGs) oxidation products were also identified using isocratic HPLC-ESI-MS. It was found that β-carotene promoted oxidation of TAGs especially at longer exposure times. For the first time two new classes of oxidized TAGs have been identified in corn oil, which were epidioxy bis-hydroperoxides and hydroxy bis-hydroperoxides. Other oxidation products of TAGs were mono-epoxides, mono-hydroperoxides, and epoxy hydroperoxides. It was found that complementing the HPLC-DAD method for β-carotene with ESI-MS method for TAGs oxidation provides a comprehensive set of analytical tools to characterize carotenoids and triacylglycerols oxidation and degradation in edible oils.