Henan Collaborative Innovation Center for Research and Development on the Whole Industry Chain of Yu-Yao, Henan University of Chinese Medicine, Zhengzhou 450046, China; Engineering Technology Research Center for Comprehensive Development and Utilization of Authentic Medicinal Materials in Henan Province, Zhengzhou 450046, China.
Henan Collaborative Innovation Center for Research and Development on the Whole Industry Chain of Yu-Yao, Henan University of Chinese Medicine, Zhengzhou 450046, China; Institute of Chinese Materia Medica, China Academy of Chinese Medical Sciences, Beijing 100700, China.
J Chromatogr A. 2024 Aug 16;1730:465100. doi: 10.1016/j.chroma.2024.465100. Epub 2024 Jun 15.
Corni fructus (CF) is always subjected to wine processing before prescription in clinic, for an enhancing effect of nourishing liver and kidney. While, the underlying mechanism for this processing on CF remains obscure. In this study, a sensitive ultra-high-performance liquid chromatography mass spectrometry (UPLC-MS/MS) method combined multi-dimensional analyses was established to monitor chemical characterizations of raw and wine-processed CF (WCF) and hence reveal the effects and underlying mechanism of wine processing on CF. As indicated, a total of 216 compounds were tentatively identified, including 98 structurally complex and variable home/hetero-polymers, that were composed of iridoid glucosides, gallic acids, caffeic acid and/or 5-HMF. Interestingly, 53 of these compounds probably characterized potential novel, including 35 iridoid glucosides or their dimers, 9 iridoid glucoside-gallic acid dimers, 7 gallic acids derivatives and 2 gallic acid-caffeic acid dimers, which provides ideas for natural product researchers. Meanwhile, the multi-dimensional analyses including principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA) and linear regression analysis were used to explore the differences between CF and WCF. The results showed that 23 compounds as chemical markers greatly contributing to the distinction were screened out, and 3 of which (7α/β-O-ethyl-morroniside, gallic acid and 5-HMF) in WCF indicated an increasing trend in intensities in relative to those in CF. Additionally, linear regression analysis showed that in WCF 53 compounds exhibited an increasing in intensities, while 132 ones did a decreasing trend, compared with those in CF. As our investigation demonstrated, acetal reaction of morroniside, ester hydrolysis in different organic acid derivatives as well as glycoside bond cleavage during wine processing probably resulted in the distinctions. The findings of this study provide a further understanding of the effect and mechanism of wine processing on CF.
山茱萸（CF）在临床上入药前通常要经过酒制，以增强补肝益肾的功效。然而，这种炮制方法对 CF 的作用机制尚不清楚。本研究建立了一种灵敏的超高效液相色谱-质谱联用（UPLC-MS/MS）方法，并结合多维分析，以监测生品和酒制品（WCF）的化学成分特征，从而揭示酒炮制对 CF 的影响及其作用机制。结果表明，共初步鉴定出 216 种化合物，包括 98 种结构复杂、变化多样的内/杂多聚物，由裂环环烯醚萜苷、没食子酸、咖啡酸和/或 5-HMF 组成。有趣的是，其中 53 种化合物可能具有潜在的新颖性，包括 35 种裂环环烯醚萜苷或其二聚体、9 种裂环环烯醚萜苷-没食子酸二聚体、7 种没食子酸衍生物和 2 种没食子酸-咖啡酸二聚体，为天然产物研究人员提供了思路。同时，采用主成分分析（PCA）、偏最小二乘判别分析（PLS-DA）和线性回归分析等多维分析方法探讨 CF 和 WCF 之间的差异。结果表明，筛选出 23 种化合物作为化学标志物，对区分具有重要贡献，其中 3 种（7α/β-O-乙基莫诺苷、没食子酸和 5-HMF）在 WCF 中的相对强度呈增加趋势。此外，线性回归分析表明，与 CF 相比，WCF 中有 53 种化合物的相对强度增加，而 132 种化合物的相对强度则呈下降趋势。本研究表明，莫诺苷的缩醛反应、不同有机酸衍生物的酯水解以及糖苷键在酒炮制过程中的裂解可能导致了这些差异。该研究结果为进一步了解酒炮制对 CF 的作用和机制提供了依据。
