Mollica Fabio, Bonoldi Lucia, Amorati Riccardo
Department of Chemistry "G. Ciamician", University of Bologna, Via S. Giacomo 11, I-40126 Bologna, Italy.
Research and Technological Innovation Department, Eni SpA, Via F. Maritano 26, I-20097 San Donato Milanese, Italy.
Antioxidants (Basel). 2022 Oct 29;11(11):2142. doi: 10.3390/antiox11112142.
Peroxidation of vegetable oils represents a major problem for the food and biodiesel industries, and it is greatly accelerated by oil degree of unsaturation and by temperature increase. Phenols represent the most common additives used to counteract oil peroxidation, however clear structure-activity relationships at high temperatures are not available. We report, herein, a kinetic study of O consumption during spontaneous peroxidation of sunflower oil at 130 °C in the presence of 18 antioxidants belonging to the main families of natural and synthetic phenols, including α-tocopherol, alkylphenols (BHT, BHA), hydroquinones (TBHD), catechols (quercetin, catechin) and gallates. Results show that TBHQ provide the best protection in terms of induction period () duration and O consumption rate. EPR spectroscopy demonstrated that the inhibition activity is negatively correlated to the stability of the phenoxyl radical of the antioxidant (A), suggesting that chain propagation with linoleate (RH) moieties A + RH → AH + R decreases the efficacy of those antioxidants forming persistent A radicals. These results provide important information to optimize the antioxidant activity of phenols and of novel phenol-based materials.
植物油的过氧化是食品和生物柴油行业面临的一个主要问题,并且它会因油的不饱和度和温度升高而大大加速。酚类是用于对抗油过氧化的最常见添加剂,然而,在高温下明确的构效关系尚不明确。在此,我们报告了在130°C下,在18种属于天然和合成酚类主要家族的抗氧化剂存在下,向日葵油自发过氧化过程中氧气消耗的动力学研究,这些抗氧化剂包括α-生育酚、烷基酚(丁基羟基甲苯、丁基羟基茴香醚)、对苯二酚(叔丁基对苯二酚)、儿茶酚(槲皮素、儿茶素)和没食子酸盐。结果表明,就诱导期()持续时间和氧气消耗速率而言,叔丁基对苯二酚提供了最佳保护。电子顺磁共振光谱表明,抑制活性与抗氧化剂(A)的苯氧自由基的稳定性呈负相关,这表明与亚油酸酯(RH)部分的链增长A + RH → AH + R降低了那些形成持久性A自由基的抗氧化剂的功效。这些结果为优化酚类和新型酚基材料的抗氧化活性提供了重要信息。