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一种通过液相色谱 - 质谱联用、电子感官和气相色谱 - 离子迁移谱区分相似中药的策略:以通关藤和鸡屎藤为例

A strategy to distinguish similar traditional Chinese medicines by liquid chromatography-mass spectrometry, electronic senses, and gas chromatography-ion mobility spectrometry: Marsdeniae tenacissimae Caulis and Paederiae scandens Caulis as examples.

作者信息

Wang Jia-Wei, Pei Zhi-Dong, Chen Yue-Hua, Li Si-Yu, Wang Tian-Min, Kang Ting-Guo, Li Na, Song Ya-Mei, Song Hui-Peng, Zhang Hui

机构信息

School of Pharmacy, Liaoning University of Traditional Chinese Medicine, Dalian, China.

Liaoning University of Traditional Chinese Medicine (Liaoning Zhongda Asset Management Co. LTD), Shenyang, China.

出版信息

Phytochem Anal. 2025 Jan;36(1):144-155. doi: 10.1002/pca.3425. Epub 2024 Jul 22.

DOI:10.1002/pca.3425
PMID:39037036
Abstract

INTRODUCTION

Marsdeniae tenacissimae Caulis (MTC), a popular traditional Chinese medicine, has been widely used in the treatment of tumor diseases. Paederiae scandens Caulis (PSC), which is similar in appearance to MTC, is a common counterfeit product. It is difficult for traditional methods to effectively distinguish between MTC and PSC. Therefore, there is an urgent need for a rapid and accurate method to identify MTC and PSC.

OBJECTIVES

The aim is to distinguish between MTC and PSC by analyzing the differences in nonvolatile organic compounds (NVOCs), taste, odor, and volatile organic compounds (VOCs).

METHODS

Liquid chromatography-mass spectrometry (LC-MS) was utilized to analyze the NVOCs of MTC and PSC. Electronic tongue (E-tongue) and electronic nose (E-nose) were used to analyze their taste and odor respectively. Gas chromatography-ion mobility spectrometry (GC-IMS) was applied to analyze VOCs. Finally, multivariate statistical analyses were conducted to further investigate the differences between MTC and PSC, including principal component analysis, orthogonal partial least squares discriminant analysis, discriminant factor analysis, and soft independent modeling of class analysis.

RESULTS

The results of this study indicate that the integrated strategy of LC-MS, E-tongue, E-nose, GC-IMS, and multivariate statistical analysis can be effectively applied to distinguish between MTC and PSC. Using LC-MS, 25 NVOCs were identified in MTC, while 18 NVOCs were identified in PSC. The major compounds in MTC are steroids, while the major compounds in PSC are iridoid glycosides. Similarly, the distinct taste difference between MTC and PSC was precisely revealed by the E-tongue. Specifically, the pronounced bitterness in PSC was proven to stem from iridoid glycosides, whereas the bitterness evident in MTC was intimately tied to steroids. The E-nose detected eight odor components in MTC and six in PSC, respectively. The subsequent statistical analysis uncovered notable differences in their odor profiles. GC-IMS provided a visual representation of the differences in VOCs between MTC and PSC. The results indicated a relatively high relative content of 82 VOCs in MTC, contrasted with 32 VOCs exhibiting a similarly high relative content in PSC.

CONCLUSION

In this study, for the first time, the combined use of LC-MS, E-tongue, E-nose, GC-IMS, and multivariate statistical analysis has proven to be an effective method for distinguishing between MTC and PSC from multiple perspectives. This approach provides a valuable reference for the identification of other visually similar traditional Chinese medicines.

摘要

引言

通关藤是一种常用的传统中药,已广泛应用于肿瘤疾病的治疗。外观与通关藤相似的鸡屎藤是一种常见的伪品。传统方法难以有效区分通关藤和鸡屎藤。因此,迫切需要一种快速准确的方法来鉴别通关藤和鸡屎藤。

目的

旨在通过分析非挥发性有机化合物(NVOCs)、味道、气味和挥发性有机化合物(VOCs)的差异来区分通关藤和鸡屎藤。

方法

采用液相色谱 - 质谱联用(LC - MS)分析通关藤和鸡屎藤的NVOCs。分别使用电子舌(E - tongue)和电子鼻(E - nose)分析它们的味道和气味。应用气相色谱 - 离子迁移谱(GC - IMS)分析VOCs。最后,进行多元统计分析以进一步研究通关藤和鸡屎藤之间的差异,包括主成分分析、正交偏最小二乘法判别分析、判别因子分析和类分析的软独立建模。

结果

本研究结果表明,LC - MS、电子舌、电子鼻、GC - IMS和多元统计分析的综合策略可有效用于区分通关藤和鸡屎藤。使用LC - MS,在通关藤中鉴定出25种NVOCs,而在鸡屎藤中鉴定出18种NVOCs。通关藤中的主要化合物是甾体类,而鸡屎藤中的主要化合物是环烯醚萜苷。同样,电子舌精确揭示了通关藤和鸡屎藤之间明显的味道差异。具体而言,已证明鸡屎藤中明显的苦味源于环烯醚萜苷,而通关藤中明显的苦味与甾体类密切相关。电子鼻分别在通关藤中检测到8种气味成分,在鸡屎藤中检测到6种气味成分。随后的统计分析发现它们气味特征存在显著差异。GC - IMS直观呈现了通关藤和鸡屎藤之间VOCs的差异。结果表明,通关藤中82种VOCs的相对含量较高,相比之下,鸡屎藤中有32种VOCs具有相似较高的相对含量。

结论

在本研究中,首次证明联合使用LC - MS、电子舌、电子鼻、GC - IMS和多元统计分析是从多个角度区分通关藤和鸡屎藤的有效方法。该方法为鉴别其他外观相似的传统中药提供了有价值的参考。

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