Institute of Biology, Department of Plant Anatomy, L. Eötvös University, Pázmány Péter sétány 1/C, Budapest 1117, Hungary.
J Chromatogr A. 2010 Mar 5;1217(10):1674-82. doi: 10.1016/j.chroma.2010.01.019. Epub 2010 Jan 18.
The mass fragmentation patterns and the characteristic behavior of the trimethylsilyl (TMS) derivatives of the dibenzylbutyrolactone-type (arctiin, arctigenin, methylarctigenin, matairesinoside, matairesinol) and those of the diphenylperhydrofurotetrahydrofurane-type (phylligenin, pinoresinol) lignans, obtained by gas chromatography-mass spectrometry (GC-MS), were presented. It was shown that upon acidic hydrolysis the dibenzylbutyrolactone-type lignans are stable while the diphenylperhydrofurotetrahydrofurane-type ones decompose. As a novelty to the field we confirmed that the fragment species of the derivatized lignan glycosides, in the presence of excess hexamethyldisilazane, leaded to their in situ derivatization. Quantification of the selective fragment ions of the TMS derivatives by GC-MS, in respect of the ions found one by one, and concerning the selective fragment ions {SFI(s)} in total, provided acceptable reproducibilities, suitable for quantitation purposes: varying between 1.20% and 6.6% relative standard deviation percentages (RSD%). For characterization of the behavior of various type of lignans, analyses were performed with the untreated and with the trifluoroacetic acid hydrolyzed plant extracts, from the same sample, in parallel, both by GC-MS and by high performance liquid chromatography-mass spectrometry, working in the positive electron ionization mode (HPLC-ESPI-MS). The analysis of lignans in fruit and leaf extracts (obtained from the Arctium, Centaurea and Forsythia plants) was confirmed both by GC-MS and by HPLC-ESPI-MS. Our multicomponent system (including the identification and quantification of sugars, sugar alcohols, and several members of various homologous series of acids, anthraquinones and flavonoids) has been extended to the analysis of lignan glycosides and to the free lignans. Reproducibilities in the quantitation of lignans in plant matrices, as averages on GC and HPLC basis, varied between 0.9% and 11% (RSD). The distribution of the lignan constituents was presented for 5 Arctium, for 8 Centaurea and for 4 Forsythia plant extracts: the total of lignan contents varied between 0.42 and 87.9 mg/g, respectively.
呈现了通过气相色谱-质谱联用技术（GC-MS）获得的二苄基丁内酯型（刺蒴麻苷、刺蒴麻苷元、甲基刺蒴麻苷元、马替瑞斯诺苷、马替瑞斯醇）和二苯并海因型（松脂素、松脂素-4'-O-β-D-葡萄糖苷）木脂素的三甲硅烷基（TMS）衍生物的质谱碎裂模式和特征行为。结果表明，酸性水解时二苄基丁内酯型木脂素稳定，而二苯并海因型木脂素则分解。作为该领域的新发现，我们证实了衍生化后的木脂素糖苷的碎片种类，在过量六甲基二硅氮烷的存在下，导致其原位衍生化。通过 GC-MS 对 TMS 衍生物的选择性碎片离子进行定量，逐个比较离子，总选择性碎片离子（SFI（s）），提供了可接受的重现性，适合定量目的：变化范围在 1.20%至 6.6%的相对标准偏差百分比（RSD%）。为了表征各种类型木脂素的行为，在同一样品中，分别平行进行未经处理和三氟乙酸水解的植物提取物的 GC-MS 和高效液相色谱-质谱分析，工作在正电子电离模式（HPLC-ESPI-MS）下。通过 GC-MS 和 HPLC-ESPI-MS 确认了果实和叶片提取物（从刺蒴麻、苍耳和连翘植物中提取）中的木脂素分析。我们的多组分系统（包括糖、糖醇和几种同源系列酸、蒽醌和类黄酮的鉴定和定量）已扩展到木脂素糖苷和游离木脂素的分析。在植物基质中木脂素定量的重现性，GC 和 HPLC 平均值在 0.9%至 11%（RSD）之间变化。为 5 种刺蒴麻、8 种苍耳和 4 种连翘植物提取物呈现了木脂素成分的分布：总木脂素含量分别在 0.42 至 87.9mg/g 之间变化。
