Determination of oleanolic, betulinic and ursolic acid in Lamiaceae and mass spectral fragmentation of their trimethylsilylated derivatives
Determination of oleanolic, betulinic and ursolic acid in Lamiaceae and mass spectral fragmentation of their trimethylsilylated derivatives
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DOI：
10.1365/s10337-008-0533-6
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发表时间：
2008-03-01
期刊：
影响因子：
1.7
通讯作者：
Voncina, Ernest
中科院分区：
文献类型：
--
作者：
Razborsek, Masa Islamcevic;Voncina, Darinka Brodnjak;Voncina, Ernest
采用气相色谱-质谱联用技术（GC-MS）对Lamiaceae科不同植物（迷迭香-迷迭香、鼠尾草-鼠尾草、冬味鼠尾草、鼠尾草-鼠尾草和粘鼠尾草-鼠尾草）的植物化学成分进行了研究。研究主要集中在齐墩果酸、白桦果酸和熊果酸。由于齐墩果酸和熊果酸是具有非常相似结构的位置异构体，一些作者报道了它们在分离和鉴定方面的困难。然而，这两种化合物都可以通过气相色谱的洗脱顺序和质谱中片段离子信号的强度来很好地区分，其中主要观察到反diels - alder反应。采用超声提取、固相萃取、粒径排除色谱、三甲基硅基化、气相色谱-质谱联用等方法对上述化合物进行分离、鉴定和定量。通过保留时间和质谱与纯标准品的比较，对化合物进行了鉴定。研究了三种衍生酸的质谱破碎行为。本文对得到的特征碎片模式进行了讨论。在1 ~ 50 mg L-1的浓度范围内，三种化合物均具有良好的线性关系。相关系数（r(2)）在0.9980 ~ 0.9983之间。定量分析表明，齐墩果酸含量为干重0.09 ~ 0.9%，白桦酸含量为微量~ 0.6%，熊果酸含量为干重0.09 ~ 1.6%。
Phytochemical investigations of different species of Lamiaceae family (rosemary-Rosmarinus officinalis L., sage-Salvia officinalis L., winter savory-Satureja montana L., clary sage-Salvia sclarea L. and sticky sage-Salvia glutinosa L.), using gas chromatography and mass spectrometry (GC-MS) were performed. The studies were focused on oleanolic, betulinic and ursolic acid. Since oleanolic and ursolic acid are position isomers with very similar structures, the difficulties in their separation and identification have been reported by several authors. However, both compounds can be well distinguished by order of elution during gas chromatography and by intensities of the fragment ion signals in their mass spectra, where the retro-Diels-Alder reaction was primarily observed. A combination of ultrasonic extraction, solid phase extraction, size exclusion chromatography, trimethylsilylation, and GC-MS resulted in simultaneous separation, identification and quantification of the mentioned compounds. The compounds have been identified by retention time and comparison of mass spectra with those of pure standards. The mass spectral fragmentation behavior of all three derivatised acids was investigated. The obtained characteristic fragment patterns are discussed in the presented work. Good linearity over the concentration range 1-50 mg L-1 for all three compounds was confirmed. The correlation coefficients (r(2)) were in the range of 0.9980-0.9983. Quantitative analyses of different Lamiaceae extracts showed that the oleanolic acid content ranged from 0.09 to 0.9% dry weight, content of betulinic acid ranged from traces to 0.6%, and that of ursolic acid varied from 0.09 to 1.6% dry weight.