Saponins are amphiphilic molecules of pharmaceutical interest and most of their biological activities (i.e., cytotoxic, hemolytic, fungicide, etc.) are associated to their membranolytic properties. These molecules are secondary metabolites present in numerous plants and in some marine animals, such as sea cucumbers and starfishes. Structurally, all saponins correspond to the combination of a hydrophilic glycan, consisting of sugar chain(s), linked to a hydrophobic triterpenoidic or steroidic aglycone, named the sapogenin. Saponins present a high structural diversity and their structural characterization remains extremely challenging. Ideally, saponin structures are best established using nuclear magnetic resonance experiments conducted on isolated molecules. However, the extreme structural diversity of saponins makes them challenging from a structural analysis point of view since, most of the time, saponin extracts consist in a huge number of congeners presenting only subtle structural differences. In the present review, we wish to offer an overview of the literature related to the development of mass spectrometry for the study of saponins. This review will demonstrate that most of the past and current mass spectrometry methods, including electron, electrospray and matrix-assisted laser desorption/ionization ionizations, gas/liquid chromatography coupled to (tandem) mass spectrometry, collision-induced dissociation including MS³ experiments, multiple reaction monitoring based quantification, ion mobility experiments, and so forth, have been used for saponin investigations with great success on enriched extracts but also directly on tissues using imaging methods.

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皂甙的质谱分析

皂甙是具有药学意义的两亲性分子，它们的大部分生物活性（即细胞毒性、溶血、杀真菌等）与其膜溶解特性有关。这些分子是存在于许多植物和一些海洋动物（如海参和海星）中的次级代谢产物。在结构上，所有皂苷都对应于亲水性聚糖的组合，由糖链组成，与疏水性三萜类或类固醇糖苷配基相连，称为皂苷元。皂苷具有高度的结构多样性，其结构表征仍然极具挑战性。理想情况下，皂苷结构最好使用对分离分子进行的核磁共振实验来建立。然而，皂苷的极端结构多样性使它们从结构分析的角度来看具有挑战性，因为在大多数情况下，皂苷提取物包含大量仅存在细微结构差异的同类物。在本综述中，我们希望概述与皂苷研究质谱法发展相关的文献。本综述将证明大多数过去和当前的质谱方法，包括电子、电喷雾和基质辅助激光解吸/电离电离、气相/液相色谱与（串联）质谱耦合、碰撞诱导解离（包括 MS）我们希望提供与用于皂苷研究的质谱法发展相关的文献概述。本综述将证明大多数过去和当前的质谱方法，包括电子、电喷雾和基质辅助激光解吸/电离电离、气相/液相色谱与（串联）质谱耦合、碰撞诱导解离（包括 MS）我们希望提供与用于皂苷研究的质谱法发展相关的文献概述。本综述将证明大多数过去和当前的质谱方法，包括电子、电喷雾和基质辅助激光解吸/电离电离、气相/液相色谱与（串联）质谱耦合、碰撞诱导解离（包括 MS）³实验、基于定量的多反应监测、离子淌度实验等，已被用于皂苷研究，在丰富的提取物上取得了巨大成功，但也使用成像方法直接在组织上进行了研究。