Mechanism of the initial oxidation of monounsaturated fatty acids
Mechanism of the initial oxidation of monounsaturated fatty acids
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单不饱和脂肪酸的初始氧化机理
DOI：
10.1016/j.foodchem.2022.133298
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发表时间：
2022-06-01
期刊：
影响因子：
8.8
通讯作者：
Li, Changmo
中科院分区：
文献类型：
--
作者：
Ding, Cong;Wang, Lu;Li, Changmo
检测技术的发展促使人们有必要详细阐述不饱和脂肪酸氧化背后的理论。本研究将单不饱和脂肪酸在60℃下氧化的检测与计算机模拟相结合，为过氧化氢和烯丙基的形成提供了先进的理论基础。结果表明，氧化反应使8-羟基过氧基-反式-9-十八烯酸(Trans8)和9-羟基过氧反式-10-十八烯酸(Trans9)和10-羟基过氧反式-8-十八烯酸(Trans10)在低温下的产率分别提高了3.4 mg/g和2.7 mg/g。过氧化氢自由基生成能为0.36kcal/mol，烯丙基异构化生成能为78.52kcal/mol，表明过氧化氢的生成存在两条途径：β-裂解和烯丙基异构化。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。这一发现为今后的脂质氧化分析提供了新的依据。
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 degrees 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-8octadecenoate (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: beta-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.