Silymarin, milk thistle (Silybum marianum) extract, contains a mixture of mostly isomeric bioactive flavonoids and flavonolignans that are extensively studied, especially for their possible liver-protective and anticancer effects. Because of the differing bioactivities of individual isomeric compounds, characterization of their proportion in a mixture is highly important for predicting its effect on health. However, because of silymarin's complexity, this is hardly feasible by common analytical techniques. In this work, ultraperformance liquid chromatography coupled with drift tube ion mobility spectrometry and quadrupole time-of-flight mass spectrometry was used. Eleven target silymarin compounds (taxifolin, isosilychristin, silychristins A and B, silydianin, silybins A and B, 2,3-cis-silybin B, isosilybins A and B and 2,3-dehydrosilybin) and five unknown flavonolignan isomers detected in the milk thistle extract were fully separated in a 14.5-min analysis run. All the compounds were characterized on the basis of their accurate mass, retention time, drift time, collision cross section and fragmentation spectra. The quantitative approach based on evaluation of the ion mobility data demonstrated lower detection limits, an extended linear range and total separation of interferences from the compounds of interest compared with the traditional approach based on evaluation of liquid chromatography-quadrupole time-of-flight mass spectrometry data. The following analysis of a batch of milk thistle-based food supplements revealed significant variability in the silymarin pattern, especially in the content of silychristin A and silybins A and B. This newly developed method might have high application potential, especially for the characterization of materials intended for bioactivity studies in which information on the exact silymarin composition plays a crucial role. Graphical Abstract.

中文翻译：

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液相色谱-漂移管离子淌度质谱是一种新的具有挑战性的工具，用于水飞蓟素黄酮木聚糖的分离和表征。

水飞蓟（Silybum marianum）提取物水飞蓟素含有主要是异构的生物活性类黄酮和黄酮木聚糖的混合物，人们对其进行了广泛研究，尤其是因为它们可能具有保肝和抗癌作用。由于各个异构化合物的生物活性不同，因此表征其在混合物中的比例对于预测其对健康的影响非常重要。但是，由于水飞蓟素的复杂性，通过常规分析技术很难做到这一点。在这项工作中，使用了超高效液相色谱结合漂移管离子迁移谱仪和四极杆飞行时间质谱仪。十一种目标水飞蓟素化合物（紫杉醇，异水飞蓟素，水飞蓟素A和B，水飞蓟素，水飞蓟宾A和B，2,3-顺水飞蓟宾B，异水飞蓟宾A和B和2，在14.5分钟的分析运行中将乳蓟提取物中检测到的5种未知的黄酮木脂素异构体和3-脱氢水飞蓟宾）完全分离。所有化合物均根据其准确的质量，保留时间，漂移时间，碰撞截面和碎片谱进行了表征。与基于液相色谱-四极杆飞行时间质谱评估的传统方法相比，基于离子迁移率数据评估的定量方法显示出较低的检测限，扩展的线性范围和对目标化合物的干扰物的完全分离数据。以下对一批基于乳蓟的食品补充剂的分析显示，水飞蓟素模式具有明显的变异性，尤其是水飞蓟素A和水飞蓟宾A和B的含量。这种新开发的方法可能具有很高的应用潜力，特别是对于旨在用于生物活性研究的材料的表征，其中有关水飞蓟素确切成分的信息起着至关重要的作用。图形概要。