Department of Pharmacognosy, Faculty of Pharmacy, Medical University-Sofia, 2 Dunav str., 1000, Sofia, Bulgaria.
Institute of Molecular Biology and Biotechnology, bul. Ruski 105, 4000 Plovdiv, Bulgaria.
J Pharm Biomed Anal. 2018 Sep 10;159:567-581. doi: 10.1016/j.jpba.2018.07.041. Epub 2018 Jul 21.
Glucuronide Oleanane-type Triterpenoid Carboxylic Acid 3, 28-Bidesmosides (GOTCAB) saponins are bioactive natural compounds spread in Caryophyllidae. The high complexity of GOTCAB occurring as closely related isobaric and positional isomers is a challenge in their separation and identification. A new liquid chromatography - high resolution Orbitrap mass spectrometry acquisition strategy would be important for the structural elucidation of GOTCAB in plant extracts. In this study, the fragmentation behaviors of GOTCAB from methanol-aqueous root extract of Gypsophila glomerata Pall ex M. B. (Caryophyllaceae) were investigated using ultra high-performance liquid chromatography (UHPLC) coupled with hybrid quadrupole-Orbitrap high resolution mass spectrometry (HRMS). A new saponin was isolated and its structure was established by 1D and 2D-NMR spectroscopic experiments as 3-O-β-D-galactopyranosyl-(1→2)-[α-L-arabinopyranosyl-(1→3)]-β-D-glucuronopyranosyl gypsogenin 28-O-α-L-arabinopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→4)]-α-L-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl ester. On the basis of the accurate mass measurements, fragmentation patterns in MS/MS analyses and comparison with previously isolated authentic references, a total of 41 GOTCAB saponins were identified or tentatively elucidated in G. glomerata roots, including 14 pairs of isobars. Possible fragmentation pathways for three groups of GOTCAB are suggested. The group I appeared to be GOTCAB of gypsogenin with two carbohydrate chains: a branched trisaccharide at C-3 and tri- to hexa-saccharide attached to C-28 of the aglycone through a deoxyhexose residue. Saponins with monoacetylated (group II) or sulphated (group III) C-28 chain were evidenced, as well as quillaic and oleanolic acid GOTCAB. Sixteen GOTCAB were previously not described. The content of Gypsophila prosaponins, gypsogenin 3-O-glucuronide (7.4079 ± 0.0723 mg/g dry weight, dw) and quillaic acid 3-O-glucuronide (4.4593 ± 0.1207 mg/g dw), was determined by solid phase extraction - high-performance liquid chromatography (SPE-HPLC). In this study is presented the first systematic investigation on the fragmentation patterns and diagnostic fingerprints of the fragment ions in the MS/MS spectra of the gypsogenin -, quillaic acid - and oleanolic acid - bidesmosides. A LC-HRMS Orbitrap acquisition strategy could give an insight in the GOTCAB containing taxa.
薯蓣皂素型三萜羧酸 3,28-双糖苷（GOTCAB）皂苷是分布在石竹科中的生物活性天然化合物。GOTCAB 作为密切相关的等质量和位置异构体存在，其复杂性很高，这给它们的分离和鉴定带来了挑战。新的液相色谱-高分辨轨道阱质谱采集策略对于植物提取物中 GOTCAB 的结构阐明将非常重要。在这项研究中，使用超高效液相色谱 (UHPLC) 结合混合四极杆-轨道阱高分辨质谱 (HRMS) 研究了来自Gypsophila glomerata Pall ex M. B.（石竹科）甲醇水根提取物中的 GOTCAB 的碎裂行为。通过 1D 和 2D-NMR 光谱实验分离并鉴定了一种新的皂苷，其结构为 3-O-β-D-半乳糖基-(1→2)-[α-L-阿拉伯吡喃基-(1→3)]-β-D-葡萄糖醛酸吡喃基 gypsogenin 28-O-α-L-阿拉伯吡喃基-(1→3)-[β-D-木吡喃基-(1→4)]-α-L-鼠李吡喃基-(1→2)-β-D-岩藻吡喃基酯。基于精确质量测量、MS/MS 分析中的碎裂模式以及与先前分离的真实参考物的比较，共鉴定或初步阐明了 41 种 GOTCAB 皂苷在 G. glomerata 根中，包括 14 对等质量体。提出了三组 GOTCAB 的可能碎裂途径。第 I 组似乎是具有两条糖链的 gypsogenin 的 GOTCAB：在糖苷配基 C-3 处的支链三糖和通过去氧己糖残基连接到 C-28 的三糖至六糖。还证实了单乙酰化（第 II 组）或硫酸化（第 III 组）C-28 链的皂苷，以及 quillaic 和齐墩果酸 GOTCAB。有 16 种 GOTCAB 以前没有描述过。通过固相萃取-高效液相色谱法（SPE-HPLC）测定 Gypsophila prosaponins、gypsogenin 3-O-葡萄糖醛酸（7.4079±0.0723 mg/g 干重，dw）和 quillaic 酸 3-O-葡萄糖醛酸（4.4593±0.1207 mg/g dw）的含量。在本研究中，首次系统研究了 gypsogenin-、quillaic 酸-和齐墩果酸-bidesmosides 的 MS/MS 光谱中碎片离子的碎裂模式和诊断指纹。LC-HRMS 轨道阱采集策略可以深入了解含 GOTCAB 的类群。
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