Frankel E N, Neff W E, Rohwedder W K, Khambay B P, Garwood R F, Weedon B C
Lipids. 1977 Nov;12(11):908-13. doi: 10.1007/BF02533310.
The gas chromatography-mass spectrometry (GC-MS) approach developed in the preceding paper was applied for qualitative and quantitative investigations of autoxidation products of methyl linoleate. A GC-MS computer summation method was standardized with synthetic 9- and 13-hydroxyoctadecanoate. Equal amounts of 9- and 13-hydroperoxides were found in all samples of linoleate autoxidized at different temperatures and peroxide levels. The results are consistent with the classical free radical mechanism of autoxidation involving a pentadiene intermediate having equivalent sites for oxygen attack at carbon-9 and carbon-13. Minor oxygenated products of autoxidation indicated by GC-MS include keto dienes, epoxyhydroxymonoenes, di- and tri-hydroxy monoenes. These hydroxy compounds are presumed to be present in the form of hydroperoxides. The quantitative GC-MS method was found suitable for the analysis of autoxidized mixtures of oleate and linoleate. By this method, it is possible to determine the origin of the hydroperoxides formed in mixtures of these fatty esters.
上一篇论文中开发的气相色谱-质谱联用（GC-MS）方法被用于亚油酸甲酯自氧化产物的定性和定量研究。用合成的9-和13-羟基十八烷酸酯对GC-MS计算机累加方法进行了标准化。在不同温度和过氧化物水平下自氧化的所有亚油酸酯样品中，均发现了等量的9-和13-氢过氧化物。这些结果与涉及具有在碳-9和碳-13处等效氧攻击位点的戊二烯中间体的经典自氧化自由基机制一致。GC-MS表明的自氧化的少量氧化产物包括酮二烯、环氧羟基单烯、二羟基和三羟基单烯。这些羟基化合物被认为以氢过氧化物的形式存在。发现定量GC-MS方法适用于油酸酯和亚油酸酯自氧化混合物的分析。通过这种方法，可以确定这些脂肪酸酯混合物中形成的氢过氧化物的来源。
