食品科学 ›› 2021, Vol. 42 ›› Issue (11): 56-62.doi: 10.7506/spkx1002-6630-20200610-137

• 基础研究 • 上一篇    下一篇

不饱和脂肪酸室温氧化过程中自由基的变化

王蒙蒙,寇宇星,周笙,王莉倩,于修烛   

  1. (1.西北农林科技大学食品科学与工程学院,陕西 杨凌 712100;2.上海交通大学农业与生物学院,上海 200240)
  • 出版日期:2021-06-15 发布日期:2021-06-29
  • 基金资助:
    “十三五”国家重点研发计划重点专项(2019YFD1002403)

Changes of Free Radicals during Oxidation of Unsaturated Fatty Acids at Room Temperature

WANG Mengmeng, KOU Yuxing, ZHOU Sheng, WANG Liqian, YU Xiuzhu   

  1. (1. College of Food Science and Engineering, Northwest A & F University, Yangling 712100, China;2. School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai 200240, China)
  • Online:2021-06-15 Published:2021-06-29

摘要: 为探究不饱和脂肪酸室温氧化过程中自由基的变化规律,本实验以油酸、亚油酸和亚麻酸为实验材料,采用电子顺磁共振和核磁共振技术,对室温氧化及外源物质影响下不饱和脂肪酸氧化过程自由基和核磁共振氢谱变化规律进行分析。结果表明:油酸氧化0~60 min期间所含自由基以烷基自由基(R·)为主,之后以烷过氧自由基(ROO·)和烷氧自由基(RO·)为主;亚油酸、亚麻酸氧化过程所含自由基均以R·为主;氧化期间脂肪酸(RH)被引发生成R·和H·,H·与ROO·结合生成氢过氧化物,部分氢过氧化物发生分解,且亚麻酸氧化和降解程度高于亚油酸和油酸;加入生育酚(tocopherol,VE)和特丁基对苯二酚(tert-butylhydroquinone,TBHQ)均可抑制RO·、ROO·等自由基的形成;加入偶氮二异庚腈(2,2’-azobis(2,4-dimethyl)valeronitrile,ADVN)的脂肪酸中所含自由基以R·为主,同时会引入无机碳中心自由基;加入叶绿素的油酸和亚麻酸组自旋总数分别在150 min和90 min明显升高,其余时间段呈波动式变化。结论:不饱和脂肪酸室温氧化过程中,不饱和程度越高的脂肪酸生成R·数量越多;加入的VE和TBHQ会提供H·,其与脂质自由基结合从而抑制链式反应进行,尤其会抑制ROO·、RO·生成;ADVN、叶绿素具有自由基引发效应,能促进链式反应进行。

关键词: 不饱和脂肪酸;室温氧化;自由基;外源物质;电子顺磁共振

Abstract: The pattern of changes in free radicals during the oxidation of unsaturated fatty acids including oleic, linoleic, and linolenic acid at room temperature was investigated by electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR). The impact of exogenous substances on it was also evaluated. The results showed that the EPR spectra of oleic acid were dominated by alkyl radicals (R·) during oxidation from 0 to 60 min and then by alkyl peroxyl radicals (ROO·) and alkoxyl radicals (RO·). The radicals formed during the oxidation of linoleic and linolenic acids were mainly R·. During the oxidation process, the fatty acids (RH) were induced to form R· and H·, and then H· combined with ROO· to generate hydroperoxides, which were partly decomposed. The oxidation and degradation of linolenic acid were higher than those of linoleic acid and oleic acid. Addition of either tocopherol (VE) or tert-butylhydroquinone (TBHQ) inhibited the formation of free radicals such as RO· and ROO·. The EPR spectra of fatty acids added with 2,2’-azobis(2,4-dimethyl)valeronitrile (ADVN) were dominated by R· during oxidation, and inorganic carbon-centered free radicals were also introduced. The total number of spins in oleic and linolenic acid added with chlorophyll significantly increased at 150 and 90 min, respectively, and was fluctuated at other times. The higher the degree of unsaturation of fatty acids, the greater the amount of R· radicals produced during oxidation. Addition of VE and TBHQ could provide H·, which combined with lipid free radicals to inhibit the process of chain reaction and particularly inhibit the generation of ROO· and RO·. ADVN and chlorophyll could have a free radical-initiating effect, thus promoting the chain reaction.

Key words: unsaturated fatty acids; room temperature oxidation; free radicals; exogenous substances; electron paramagnetic resonance

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