Campanella Luigi, Nuccilli Adriano, Tomassetti Mauro, Vecchio Stefano
Department of Chemistry, "La Sapienza" University of Rome, P.le A. Moro 5, I-00185 Rome, Italy.
Talanta. 2008 Feb 15;74(5):1287-98. doi: 10.1016/j.talanta.2007.08.036. Epub 2007 Sep 5.
The process of artificial rancidification of extra-virgin olive oil due to heating in an oxidizing atmosphere was studied by testing an actual kinetic model of the process and monitoring the thermal oxidative degradation of the polyphenols contained in it. To this end, a series of oxidative degradation experiments were carried out on extra-virgin olive oil samples under isothermal conditions at 98, 120, 140, 160, and 180 degrees C using a thermostatic silicon oil bath. The experimental procedure used in this study carefully followed the recommendations regarding the study of olive oil rancidification set out in the AOM procedure. The change in polyphenol concentration with time was monitored at selected temperatures using a tyrosinase biosensor operating in an organic phase (n-hexane). The activation energy for the polyphenol degradation process determined using the MacCallum method was found to be practically constant throughout most of the process. Furthermore, the application of the so-called "model-fitting" method to this process enabled the specific constant rates to be determined at the above-mentioned selected temperatures. In addition, a confirmation of the activation energy value was obtained by the "model-fitting" method and the algorithm of the kinetic model equation best-fitting the experimental curve representing the whole process was checked. Finally, further very interesting observations were made, for instance, the half-life concentration values of polyphenols at selected temperatures between 98 and 180 degrees C.
通过测试该过程的实际动力学模型并监测其中所含多酚的热氧化降解,研究了特级初榨橄榄油在氧化气氛中加热导致的人工酸败过程。为此,使用恒温硅油浴在98、120、140、160和180摄氏度的等温条件下,对特级初榨橄榄油样品进行了一系列氧化降解实验。本研究中使用的实验程序严格遵循了美国油脂化学家协会(AOM)程序中关于橄榄油酸败研究的建议。使用在有机相(正己烷)中运行的酪氨酸酶生物传感器,在选定温度下监测多酚浓度随时间的变化。发现使用麦卡勒姆方法确定的多酚降解过程的活化能在整个过程的大部分时间内几乎保持恒定。此外,将所谓的“模型拟合”方法应用于该过程,可以确定上述选定温度下的特定恒定速率。此外,通过“模型拟合”方法获得了活化能值的确认,并检查了最适合代表整个过程的实验曲线的动力学模型方程的算法。最后,还进行了一些非常有趣的观察,例如,在98至180摄氏度之间选定温度下多酚的半衰期浓度值。