Inhibition of Hydroperoxy-, Keto- and Hydroxy-FAME by Alpha- and Delta-Tocopherol at Rancimat Conditions

• Published in: Journal of the American Oil Chemists' Society 2016, Vol.93 (1), p.93-103
• Main Authors: Marmesat, Susana, Morales, Arturo, Ruiz-Méndez, M. Victoria, Márquez-Ruiz, Gloria, Velasco, Joaquín
• Format: Article
• Language: English
• Subjects: Agriculture; air; alpha-tocopherol; Antioxidants; Biomaterials; Biotechnology; Chemistry; Chemistry and Materials Science; chemists; delta-tocopherol; Esters; fatty acid methyl esters; Fatty acids; Food Science; Hydroperoxides; Hydroxydienes; Industrial Chemistry/Chemical Engineering; Ketodienes; Liquid chromatography; oleic acid; Original Paper; Oxidation; protective effect; Rancimat; Sunflower oil; Tocopherol; Vegetable oils
• ISSN: 0003-021X; 1558-9331
• DOI: 10.1007/s11746-015-2748-7

The effects of α- and δ-tocopherol on inhibition of hydroperoxides, keto and hydroxy compounds under Rancimat conditions, i.e. 100 °C and air bubbling, were studied in samples of fatty acid methyl esters (FAME) obtained from high linoleic (HL) and high oleic (HO) sunflower oils. Primary hydroperoxides from methyl linoleate and methyl oleate and secondary keto and hydroxy compounds derived from methyl linoleate hydroperoxides were analyzed by HPLC–UV-ELS. Different tocopherol concentrations, namely, 10, 50, 100, 500 and 1000 mg/kg, were tested. Irrespective of the lipid substrate and the initial concentration of tocopherol, results showed that the content of hydroperoxides accumulated during the induction period was remarkably higher in the samples containing δ-tocopherol. The relative concentrations of oleate hydroperoxides in the HO samples were also higher in the presence of δ-tocopherol. α-Tocopherol was more effective in inhibiting hydroperoxides at low levels, with 100 mg/kg as optimal concentration, while δ-tocopherol displayed optimal protection at 1000 mg/kg. Under the oxidation conditions applied, neither α- nor δ-tocopherol showed a protective effect on hydroperoxide decomposition at any level assayed. Formation of keto- and hydroxy-dienes was more related to the concentration of their hydroperoxide precursors. Furthermore, both tocopherols gave rise to increased concentrations of ketodienes at 500 and 1000 mg/kg compared to the controls. Such an effect was more pronounced for α-tocopherol and in the HL samples.