[心得] 精油稳定性的影响因素(二)

楼主: antioxidant (0.0)   2016-08-24 13:14:59
4.金属污染
精油储存在金属容器中,容器的不纯物会释放到精油里头[1]。和光线、高温一样,
重金属特别是铜和铁,会加速精油的自氧化,尤其存在过氧化氢时更快[2-3],铁和铜离
子会催化过氧化氢分解,产生自由基,加速自由基氧化反应。铁离子还会反应生成单态氧
,进而激发后续的光氧化反应[3]。
5.湿度
柠檬醛在水溶液中会进行酸催化反应,生成对异丙基甲苯、三甲基苯甲醇
(p-cymene-8-ol)、二甲基苯乙烯(α-p-dimethylstyrene)、甲基苯乙酮
(methylacetophenone)和甲酚(cresol) [4]。不过 Rajeswara [5]有不同结果,不同油储
存在含水的环境没有任何改变,即便水含量到20%也一样。Kaul [6]建议精油在萃取完成
后可以添加一些能抓水的成分再保存,实验显示天竺葵精油存在微量水的情况下在室温保
存一年,芳樟醇(linalool)和香叶醇(geraniol)含量减少,香茅醇(citronellol)和甲酸
香叶草酯(geranyl formate)则增加,不过瓶子里的精油只有半满,所以成分的改变可能
不完全是含有微量水的关系,瓶子里的氧气也对实验产生了影响。
6.精油的组成成分和化学结构[1]
带有烯丙基结构的分子较有可能发生自氧化反应,因为此种结构容易被抓掉一个氢原
子而形成稳定的自由基分子[7]。富含不饱和单萜烯和倍半萜的松油、松节油
(turpentine oil)在储存过程中,很快地成分就产生了变化[8]。此外,具有推电子基或
多烷基取代的分子,都会借由超共轭效应(hyperconjugation effect)来增强碳原子和过
氧化物间的键结,进而帮助稳定过氧化物并在随后反应生成过氧化氢[9]。
另外,每个分子发生的变化都有可能影响其他分子的稳定性[10],活性氧在分子间
的转移,可使易氧化的分子发生自氧化,生成较稳定的产物。换句话说,易氧化的分子就
是抗氧化物,利用自身的氧化来避免其他物质被氧化,酚类如香芹酚(carvacrol)、百里
酚(thymol)或丁香酚(eugenol)都能中止或延迟正发生的自氧化反应[1]。抗氧化能力强弱
取决于酚基上氢原子多容易被抓走,氢被抓走后,抗氧化分子形成自由基,利用自身结构
来保持稳定,这些抗氧化物能清除带有烷基、烷氧基和过氧基的自由基,提高这些分子的
稳定性[11-12],事实上,百里香精油含有80%以上的酚类,良好稳定性其来有自[8、
13-14]。精油的组成环境可能会影响里头个别分子的稳定性[2],Hagvall [15]比较乙酸
芳樟酯(linalyl acetate)、芳樟醇(linalool)和 β-石竹烯在薰衣草精油里以及未在精
油里的自氧化差异,虽然他最后总结薰衣草精油对里头分子并没有保护作用,但根据他的
实验条件,为了检测过氧化氢,让实验处在非常剧烈的氧化环境下,这可能超出精油本身
所能提供的保护范围内,因此Hagvall的结论不一定正确。
其实,我们观察到的精油变化常不是单一因素影响,而是多种因素造成的结果,所以
才常有一些矛盾的结论发生,Guenther [2]可能是依据高温时的酸催化反应,而认为湿度
对精油衰败的影响比光线来的大,但他的推测并没有得到过往文献的支持。此外,
Wabner [16]和Nasel [17]根据保存在冰箱的茶树精油含大量过氧化物,建议人们不要把
精油冰在冰箱,不过其他研究显示,在室温时,精油的降解反而在加速进行[13-14、
18-19]。总之,大部分文献所描述的精油降解都来自于光或温度,或在氧存在下,光和温
度的综合反应[20 -22]。Pfannhauser [23]指出,当在4~20℃时,光对精油稳定性影响大
过温度,Carmona [24]和El-Wakeil [18]也认为,在60和25℃,其温度影响分别高于紫外
光和日光。Karlberg [25]证明封盖储存在低温阴暗的环境下,经过一年仍能防止自氧化
的发生,所以温度、光和氧气对精油稳定性的影响都同等重要。
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