The MOE Key Laboratory of Standardization of Chinese Medicines, Shanghai Key Laboratory of Compound Chinese Medicines, and SATCM Key Laboratory of New Resources and Quality Evaluation of Chinese Medicines, Institute of Chinese Materia Medica, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China; Institute of Interdisciplinary Integrative Medicine Research, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China.
Shaanxi Collaborative Innovation Center of Chinese Medicine Resources Industrialization/State Key Laboratory of Research & Development of Characteristic Qin Medicine Resources (Cultivation) /Shaanxi Innovative Drug Research Center, Shaanxi University of Chinese Medicine, Xianyang 712083, China.
Phytomedicine. 2022 Aug;103:154223. doi: 10.1016/j.phymed.2022.154223. Epub 2022 Jun 3.
Panax notoginseng, a valuable medicinal plant, is traditionally used to treat trauma, body pain, and cardiovascular diseases in two clinical forms including raw (crude) and processed form. Processing-triggered compound transformation is responsible for the distinct bioactivity between raw and processed Panax notoginseng. Nevertheless, investigating the chemical diversity and dynamic transformation pattern of processed Panax notoginseng is challenging.
A new approach, which integrates multi-components characterization, processing trajectory depiction, discovery of differential markers, transformation mechanism of metabolites, in situ spatial distribution and transformation of metabolites, was established to elucidate the role of processing on the holistic chemical transformations of Panax notoginseng (PN).
In this study, 136 ginsenosides (mainly rare ginsenosides) were identified or tentatively characterized and the temperature-dependent chemical variation trajectory was depicted via principal component analysis (PCA). Nineteen processing-associated markers were confirmed by orthogonal partial least squares-discriminant analysis (OPLS-DA). For the first time, the transformation pathway of ginsenosides during processing were elucidated by integrating the precursor ion scan (PIS) and mimic processing strategy that involves with deglycosylation, dehydration, hydration, acetylation, and isomerization. Results of mass spectrometry imaging (MSI) revealed the major ginsenosides M-Rb1, R1, Rg1, Rb1, Rd, and Re exhibited distinct spatial distribution pattern that are highly abundant in the xylem and showed a downward trend during processing. We firstly depicted the spatial distribution of processing-triggered rare ginsenosides (Rg3, Rk1, Rg5, etc.), and in situ transformation of ginsenosides was discovered in the process of steaming. Additionally, this variation trend was consistent with untargeted metabolomics results.
This study comprehensively revealed chemical diversity and dynamic transformation pattern and depicted the spatial distribution of ginsenosides of PN during processing. It could provide a clue for the distinct bioactivities between raw and processed PN and elucidate the role of processing on the holistic chemical transformations of natural products, more importantly, the proposed strategy is valuable for the quality evaluation and control of the processing of natural product.
三七是一种珍贵的药用植物,传统上用于治疗创伤、身体疼痛和心血管疾病,有生用和炮制品两种临床形式。炮制引发的化合物转化是生三七和炮制品三七生物活性不同的原因。然而,研究炮制三七的化学成分多样性和动态转化模式具有挑战性。
本研究建立了一种新的方法,将多成分特征描述、炮制轨迹描绘、差异标志物的发现、代谢物转化机制、代谢物的原位空间分布和转化相结合,阐明炮制对三七整体化学转化的作用。
本研究共鉴定或推测出 136 个(主要为稀有皂苷)人参皂苷,并通过主成分分析(PCA)描绘了温度依赖性的化学变化轨迹。通过正交偏最小二乘判别分析(OPLS-DA),确定了 19 个炮制相关标志物。首次通过整合前体离子扫描(PIS)和模拟炮制策略(包括去糖基化、脱水、水合、乙酰化和异构化),阐明了炮制过程中人参皂苷的转化途径。质谱成像(MSI)结果表明,主要人参皂苷 M-Rb1、R1、Rg1、Rb1、Rd 和 Re 表现出明显的空间分布模式,在木质部中含量丰富,且在炮制过程中呈下降趋势。我们首次描绘了炮制诱导的稀有皂苷(Rg3、Rk1、Rg5 等)的空间分布,并发现了在蒸制过程中人参皂苷的原位转化。此外,这种变化趋势与非靶向代谢组学结果一致。
本研究全面揭示了三七在炮制过程中的化学成分多样性和动态转化模式,描绘了其在炮制过程中的人参皂苷的空间分布。这为生三七和炮制品三七生物活性的差异提供了线索,并阐明了炮制对天然产物整体化学转化的作用,更重要的是,所提出的策略对于天然产物炮制的质量评价和控制具有重要价值。