State Key Laboratory of Food Nutrition and Safety, College of Food Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457, China.
State Key Laboratory of Food Nutrition and Safety, College of Food Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457, China.
Food Chem. 2022 Oct 30;392:133298. doi: 10.1016/j.foodchem.2022.133298. Epub 2022 May 23.
The development of detection technology prompts the need to elaborate on the theory behind the oxidation of unsaturated fatty acids. This study integrates the detection of monounsaturated fatty acid oxidation at 60 °C with computational simulations to provide an advanced theoretical basis for the formation of hydroperoxides and allyl. The results indicate that oxidation reaction led to increases of 3.4 mg/g for 8-hydroperoxy-trans-9-octadecenoate (trans8) and 2.7 mg/g for 9-hydroperoxy-trans-10-octadecenoate (trans9) and 10-hydroperoxy-trans-8-octadecenoate (trans10) despite low temperatures. The energy of peroxyl radical production was 0.36 kcal/mol and that of allylic isomerization was 78.52 kcal/mol, indicating the existence of two pathways for hydroperoxides formation: β-fragmentation and the allylic isomerization. Structural equation modeling (SEM) verified the multistep competitive side reactions that occurred during oxidation. This finding provides a new basis for future analysis of lipid oxidation.
检测技术的发展促使人们需要详细阐述不饱和脂肪酸氧化背后的理论。本研究将 60°C 下的单不饱和脂肪酸氧化检测与计算模拟相结合，为氢过氧化物和烯丙基的形成提供了先进的理论基础。结果表明，尽管温度较低，但氧化反应导致 8- 氢过氧 - 反式 -9- 十八碳烯酸（反式 8）和 9- 氢过氧 - 反式 -10- 十八碳烯酸（反式 9）以及 10- 氢过氧 - 反式 -8- 十八碳烯酸（反式 10）的含量分别增加了 3.4mg/g 和 2.7mg/g。过氧自由基生成的能量为 0.36kcal/mol，烯丙基异构化的能量为 78.52kcal/mol，这表明氢过氧化物的形成存在两条途径：β- 断裂和烯丙基异构化。结构方程模型（SEM）验证了氧化过程中发生的多步竞争副反应。这一发现为未来分析脂质氧化提供了新的基础。
