Mukai Kazuo, Ohara Ayaka, Ito Junya, Hirata Masayuki, Kobayashi Eri, Nakagawa Kiyotaka, Nagaoka Shin-Ichi
Department of Chemistry, Faculty of Science, Ehime University.
Food and Biodynamic Chemistry Laboratory, Graduate School of Agricultural Science, Tohoku University.
J Oleo Sci. 2019 Jan 1;68(1):21-31. doi: 10.5650/jos.ess18179. Epub 2018 Dec 12.
A kinetic study of the reaction of singlet oxygen (O) with eight vegetable oils 1-8 containing different concentrations of tocopherols (Tocs) and tocotrienols (Toc-3s) was performed. The second-order rate constants (k) for the reaction of O with vegetable oils 1-8 (rice bran, perilla, rape seed, safflower, grape seed, sesame, extra virgin olive, and olive oils) were measured in ethanol/chloroform/DO (50:50:1, v/v/v) solution at 35°C using UV-vis spectrophotometry. Furthermore, comparisons of k values determined for the above oils 1-8 with the sum of the product {∑k [AO-i]/10} of the k values obtained for each antioxidant (AO-i) and concentration (in mg/100 g) ([AO-i]/10) of AO-i (Tocs and Toc-3s) contained in the oils 1-8 were performed. The observed k values were not reproduced by the k values calculated using only the concentrations of the four Tocs and Toc-3s. These results suggest that the contribution of fatty acids contained in the oils 1-8 is also necessary to fully explain the k values. Recently, the second-order rate constants (k) for the reaction of aroxyl radical (ArO・) with the same vegetable oils 1-8 were measured in the same solvent at 25℃ using stopped-flow spectrophotometry (Ref. 23). The k values obtained could be well explained as the sum of the product {Σ k [AO-i]/10} of the k and the [AO-i]/10 of AO-i (Tocs and Toc-3s) contained in the vegetable oils.
对单线态氧(O)与八种含有不同浓度生育酚(Toc)和生育三烯酚(Toc-3)的植物油1-8的反应进行了动力学研究。在35℃下,使用紫外可见分光光度法在乙醇/氯仿/DO(50:50:1,v/v/v)溶液中测量了O与植物油1-8(米糠油、紫苏油、菜籽油、红花油、葡萄籽油、芝麻油、特级初榨橄榄油和橄榄油)反应的二级速率常数(k)。此外,将上述植物油1-8的k值与植物油1-8中所含每种抗氧化剂(AO-i)的k值与其浓度(mg/100g)([AO-i]/10)的乘积之和{∑k[AO-i]/10}进行了比较。仅使用四种Toc和Toc-3的浓度计算得到的k值无法重现观察到的k值。这些结果表明,植物油1-8中所含脂肪酸的贡献对于充分解释k值也是必要的。最近,使用停流分光光度法在25℃下于相同溶剂中测量了芳氧基自由基(ArO・)与相同植物油1-8反应的二级速率常数(k)(参考文献23)。得到的k值可以很好地解释为植物油中所含AO-i(Toc和Toc-3)的k值与其[AO-i]/10的乘积之和{Σk[AO-i]/10}。