Analytical and Bioanalytical Chemistry ( IF 3.8 ) Pub Date : 2021-09-03 , DOI: 10.1007/s00216-021-03615-x Fengwei Ma 1, 2, 3 , Huayong Lou 1, 2 , Yonghui Ge 3 , Jinyu Li 1, 2 , Chao Chen 1, 2 , Su Xu 3 , Lei Tang 1 , Weidong Pan 1, 2
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Vulgarisins are members of diterpenoids with rare 5/6/4/5 ring skeleton from Prunella vulgaris Linn. (P. vulgaris). Their molecular scaffolds comprise different hydroxylation and degree of esterification. Vulgarisins have attracted many attentions in the fields of food and medicine for their potent bioactivities. Firstly, four reference compounds were analyzed by higher-energy collisional dissociation mass spectrometry (HCD MS/MS) and the fragmentation patterns for molecular scaffold were summarized. And then, a high-performance liquid chromatography/electrospray ionization/high-resolution mass spectrometry (HPLC-ESI-HR-MS) method was adopted to investigate the P. vulgaris extracts. Finally, the proposed analysis results were successfully applied to facilitate the discovery of the vulgarisins analogues from P. vulgaris. For the four reference compounds, the sodium adduct was the predominate ion in full scan. A specific fragmentation pathway of [M+Na]+ ions leads to produce diagnostic ions of vulgarisins at m/z 325 under HCD, which was formed through consecutive-side chains lost. Twenty-three diterpenoids, including 18 vulgarisins analogues, were identified or tentatively characterized in the botanical extracts of P. vulgaris based on their elemental constituents and characteristic fragment ion profiles. Two new vulgarisins analogues in the plant were isolated and their structures were illustrated based on extensive spectroscopic analysis using 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. The HCD MS/MS method, including the profiles of the diagnostic ions induced by characteristic fragmentation, is an effective technique for the discovery of vulgarisins analogues in P. vulgaris. The expected fragmentation pattern knowledge will also facilitate the analysis of other natural products.
Graphical abstract
中文翻译：
使用碰撞解离质谱法对普通苷进行非靶向分析，以从夏枯草中发现类似物
Vulgarisins 是二萜类化合物的成员，具有罕见的 5/6/4/5 环骨架，来自Prunella vulgaris Linn。（P。寻常）。它们的分子支架包括不同的羟基化和酯化度。普通话因其强大的生物活性而在食品和医药领域引起了广泛关注。首先，通过高能碰撞解离质谱 (HCD MS/MS) 分析了四种参考化合物，并总结了分子支架的碎裂模式。然后，采用高效液相色谱/电喷雾电离/高分辨质谱（HPLC-ESI-HR-MS）方法对P . 寻常的提取物。最后，所提出的分析结果成功地应用于促进从P 中发现普通素类似物。寻常的。对于四种参考化合物，钠加合物是全扫描中的主要离子。[M+Na] +离子的特定裂解途径导致在 HCD 下在m / z 325处产生寻常素的诊断离子，这是通过连续丢失的侧链形成的。在P的植物提取物中鉴定或初步表征了 23 种二萜，包括 18 种普通苷类似物。寻常的基于它们的元素成分和特征碎片离子分布。分离出植物中的两种新的普通素类似物，并基于使用1 D 和2 D 核磁共振 (NMR) 光谱的广泛光谱分析说明了它们的结构。HCD MS/MS 方法，包括特征性碎裂诱导的诊断离子分布图，是一种有效的技术，可用于发现P 中的普通素类似物。寻常的。预期的碎片模式知识也将有助于其他天然产物的分析。
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