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基于电子鼻、电子舌、液相色谱-高分辨四极杆飞行时间串联质谱以及电化学指纹图谱融合方法鉴别外观相似的有毒植物和药用植物(对比)

Discrimination of poisonous and medicinal plants with similar appearance ( vs) via a fusion method of E-nose, E-tongue, LC-HR-Q-TOF-MS/MS, and electrochemical fingerprint spectra.

作者信息

Zhang Xin-Ru, Chen Yue-Hua, Zhang Jia-Nuo, Wang Wen-Yu, Sun Rui-Bo, Ding Zi-Xuan, Zhang Hui, Xie Ming, Kang Ting-Guo, Song Hui-Peng

机构信息

Key Laboratory for Identification and Quality Evaluation of Traditional Chinese Medicine of Liaoning Province, Liaoning University of Traditional Chinese Medicine, Dalian, China.

Key Laboratory of Ministry of Education for TCM Viscera-State Theory and Applications, Liaoning University of Traditional Chinese Medicine, Shenyang, China.

出版信息

Front Chem. 2025 Apr 29;13:1578126. doi: 10.3389/fchem.2025.1578126. eCollection 2025.

Abstract

INTRODUCTION

The similarity in appearance of poisonous and medicinal plants, such as Asarum heterotropoides (AH) and Cynanchum paniculatum (CP), poses safety risks due to frequent confusion. Since AH contains toxic ingredients, the traditional methods of olfactory and gustatory identification cannot be used to distinguish AH from CP.

METHODS

To differentiate them systematically, we proposed a novel strategy based on dual electronic sensors (DES) and dual fingerprint spectra (DFS). The DES included two intelligent sensors, namely the E-nose and E-tongue, which differentiated AH and CP based on odor and taste, respectively. DFS comprised chemical fingerprint spectra obtained through LC-HR-Q-TOF-MS/MS and electrochemical fingerprint spectra derived from the Belousov-Zhabotinsky reaction, differentiating AH and CP by their specific and overall compositions, respectively. To our knowledge, this was the first time that the E-nose, E-tongue, LC-HR-Q-TOF-MS/MS, and the Belousov-Zhabotinsky reaction were combined to identify AH and CP.

RESULTS AND DISCUSSION

With the E-nose, we identified 25 major odor components in AH and 12 odor components in CP in a single run of 140 s. Using the E-tongue, bitterness and astringency were identified as their primary taste differences. Furthermore, 91 compounds in AH and 90 compounds in CP were identified through LC-HR-Q-TOF-MS/MS. Both AH and CP shared nitrogenous compounds, volatile oils, organic acids, and lignans. However, AH uniquely contained coumarins and flavonoids, while CP contained steroidal compounds and saccharides. Notably, AH also possessed distinct toxic components, specifically aristolactam I, aristolochic acid D, and safrole. Based on the Belousov-Zhabotinsky reaction, we obtained the electrochemical fingerprint spectra of AH and CP, thereby facilitating further distinction between these two herbs. Through the combination of electrochemical fingerprint spectra with principal component analysis (PCA) or orthogonal partial least squares-discriminant analysis (OPLS-DA), the accuracy of this method reached 100%. Through the fusion strategy, the odors, tastes, components, and electrochemical properties of AH and CP have been systematically analyzed.

摘要

引言

细辛(AH)和徐长卿(CP)等有毒植物与药用植物在外观上相似,因常被混淆而带来安全风险。由于细辛含有有毒成分,传统的嗅觉和味觉鉴别方法无法用于区分细辛与徐长卿。

方法

为系统区分二者,我们提出了一种基于双电子传感器(DES)和双指纹图谱(DFS)的新策略。DES包括两个智能传感器,即电子鼻和电子舌,分别基于气味和味道区分细辛与徐长卿。DFS包括通过液相色谱-高分辨-四极杆-飞行时间串联质谱(LC-HR-Q-TOF-MS/MS)获得的化学指纹图谱以及源自贝洛索夫-扎博京斯基反应的电化学指纹图谱,分别通过其特定成分和整体成分区分细辛与徐长卿。据我们所知,这是首次将电子鼻、电子舌、LC-HR-Q-TOF-MS/MS和贝洛索夫-扎博京斯基反应结合用于鉴别细辛与徐长卿。

结果与讨论

利用电子鼻,在140秒的单次运行中,我们鉴定出细辛中的25种主要气味成分和徐长卿中的12种气味成分。使用电子舌,苦味和涩味被确定为它们主要的味道差异。此外,通过LC-HR-Q-TOF-MS/MS鉴定出细辛中的91种化合物和徐长卿中的90种化合物。细辛和徐长卿都含有含氮化合物、挥发油、有机酸和木脂素。然而,细辛独特地含有香豆素和黄酮类化合物,而徐长卿含有甾体化合物和糖类。值得注意的是,细辛还含有独特的有毒成分,特别是马兜铃内酰胺I、马兜铃酸D和黄樟素。基于贝洛索夫-扎博京斯基反应,我们获得了细辛和徐长卿的电化学指纹图谱,从而便于进一步区分这两种草药。通过将电化学指纹图谱与主成分分析(PCA)或正交偏最小二乘判别分析(OPLS-DA)相结合,该方法的准确率达到了100%。通过融合策略,对细辛和徐长卿的气味、味道、成分和电化学性质进行了系统分析。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/97af/12069418/570467da6dc7/fchem-13-1578126-g001.jpg

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