内部萃取电喷雾电离质谱法快速鉴别人参

Rapid Identification of Different Types of Ginseng Samples by Internal Extractive Electrospray Ionization Mass Spectrometry

  • 摘要: 人参为我国珍贵传统药材,药食同源历史逾千年,被誉为“草药之王”,其药理功效受种植及加工条件的影响,品种与商品等级是决定人参质量及疗效的核心因素。为解决传统分析方法的局限,本文采用内部萃取电喷雾电离(iEESI)技术直接、快速获取人参内部组分的丰富化学信息,结合串联质谱分析和标准品比对,共鉴定出包括人参皂苷在内的25种成分。同时,采用正交偏最小二乘判别(OPLS-DA)法进行判别聚类分析,成功实现了对不同品种、不同商品规格的13类人参样本的区分,并筛选出可同时区分13类人参样本的差异性标志物(如糖类、人参皂苷等)。本方法具有无需样品预处理、快速、实时、原位等优点,有效实现了人参所含化学成分及含量的直接分析,为阐释不同类型人参的药效差异提供了方法参考。

     

    Abstract: Ginseng is a precious traditional Chinese medicinal herb with over a thousand years of nutritional and medicinal application history. Known as the “King of Herbs”, its pharmacological effects exhibit significant variation, which stems from diverse planting and post-harvest conditions, including geographical origin, growing years, cultivation methods, and processing (e.g., fresh preservation and drying). The variety and commercial grade of ginseng are the core factors determining its quality and therapeutic efficacy. Therefore, the rapid and accurate identification of these attributes is crucial for ensuring the safety and efficacy of its clinical applications. To overcome the inherent limitations of traditional analytical methods, this study proposed a rapid identification method for ginseng based on internal extraction electrospray ionization mass spectrometry (iEESI-MS). This innovative technique enabled the direct acquisition of comprehensive chemical information from intact ginseng tissue without any sample pretreatment. The working principle is as follows: a charged extractant (methanol containing 0.5 mmol/L ammonium chloride) is infused into ginseng tissue to selectively extract bioactive compounds, which are then ionized and detected by the mass spectrometer. Using tandem mass spectrometry (MS/MS) analysis, combined with precise comparison against standards (including ginsenosides Rb1, Re, and Rg1) and cross-referencing with published literature, 25 chemical components were successfully identified in ginseng. To classify different ginseng samples, a classification model was constructed using orthogonal partial least squares discriminant analysis (OPLS-DA), a supervised multivariate statistical method. The OPLS-DA model effectively distinguished 13 types of ginseng samples, including 4 major varieties (garden ginseng, forest ginseng, Korean ginseng and red ginseng) and 3 commercial grades (small, medium and large) within each variety. This model has excellent predictive performance. In conclusion, this method has the advantages of no sample pretreatment, rapid analysis, and in-situ detection. By directly extracting chemical information from within plant tissues, this method not only facilitates direct comparison of different ginseng varieties and commercial grades, but also provides a material basis for elucidating the differences in their therapeutic efficacy.

     

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