Heat flux differential scanning calorimetry (DSC) and electron spin resonance spectroscopy (ESR) were used to assess the activity and the thermal stability of antioxidants in four vegetable oils. Sunflower oil (SO) and high oleic sunflower oil (HOSO), both rich in diunsaturated fatty acids (FA), low trans oil (LT) and partially hydrogenated palm oil (PHPO), both containing monounsaturated FA, were analyzed by isothermal heat flux DSC, with or without 300 mg/kg of antioxidant: ascorbyl palmitate (AP), alpha-tocopherol (alpha T), delta-tocopherol (delta T) and propyl gallate (PG). DSC experiments showed that delta T is the most effective antioxidant for SO and PG for the less unsaturated oils. SO and PHPO were also analyzed by ESR at 120 and 145 degrees C, respectively. ESR results confirm the strongest antioxidant activity of delta T and PG for SO and PHPO, respectively. Therefore, the present study demonstrates that DSC and ESR are valuable technologies to study activity and stability of antioxidants at high temperature. Moreover, experiments performed in the presence of the spin-trap N-tert-butyl-alpha-phenylnitrone (PBN), suggest that delta T delay lipid oxidation through a different reaction mechanism when compared to alpha T. A different mechanism between tocopherols isomers in delaying lipid oxidation has been hypotized. (c) 2006 Elsevier Ltd. All rights reserved.