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Extreme Kinetics of Chemiluminescence in the Initiated Oxidation of Vegetable Lipids
Russian Journal of Physical Chemistry B ( IF 1.4 ) Pub Date : 2020-07-31 , DOI: 10.1134/s1990793120030264
R. F. Vasil’ev , V. D. Kancheva , V. V. Naumov , A. K. Slavova-Kazakova , A. V. Trofimov , G. F. Fedorova , O. I. Yablonskaya

Abstract

During the oxidation of sunflower oil initiated by 2,2'-azo-bis-isobutyronitrile, which was used in this study as the model lipid system of plant origin, the previously unobserved form of kinetic chemiluminescence curves has been discovered. At the end of the induction period, during which chemiluminescence was suppressed by the antioxidants present in sunflower oil, instead of the expected smooth S-shaped output of the luminescence intensity at a significantly higher stationary level, a sharp surge in intensity was observed with its subsequent decrease to the stationary level. The standard kinetic scheme, which is used in most works on the effect of antioxidants on chemiluminescence in the chain free-radical oxidation of hydrocarbons, cannot explain the shape of the obtained kinetic curves. To explain the discovered phenomenon, an extended kinetic scheme, which takes into account the reactions of the initiator isobutyronitrile-peroxide radicals and their conversion to methyl-peroxide radicals, is proposed. It is shown that the observed extreme kinetics is possible only in the case of quantum yields of the chemiluminescence from the reaction of the initiator isobutyronitrile-peroxide radicals with the substrate peroxide radicals, which are 1–2 orders of magnitude higher than the quantum yields of other chemiluminescent reactions.


中文翻译:

植物脂质引发氧化过程中化学发光的极端动力学。

摘要

在由2,2'-偶氮-双-异丁腈引发的葵花籽油氧化过程中,该氧化被用作本研究的植物来源模型脂质系统,动力学化学发光曲线以前未被发现。在诱导期结束时,向日葵油中存在的抗氧化剂抑制了化学发光,而不是在稳定水平明显高的情况下,发光强度没有预期的平滑S形输出,观察到强度急剧上升。随后下降到固定水平。在大多数工作中使用的标准动力学方案无法说明抗氧化剂对烃链自由基氧化中化学发光的影响,该动力学方案无法解释所得动力学曲线的形状。为了解释发现的现象,提出了一种扩展的动力学方案,该方案考虑了引发剂异丁腈-过氧化物自由基的反应及其向过氧化甲基自由基的转化。结果表明,只有在引发剂异丁腈-过氧化物自由基与底物过氧化物自由基反应产生化学发光的量子产率的情况下,观察到的极端动力学才是可能的,该化学发光的量子产率比α-羟基的量子产率高1-2个数量级。其他化学发光反应。
更新日期:2020-07-31
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