Detection of Adulterated Naodesheng Tablet ( Naodesheng Pian ) via In-Depth Chemical Analysis and Subsequent Reconstruction of Its Pharmacopoeia Q-Markers

• Published in: Molecules (Basel, Switzerland) Vol. 29; no. 6; p. 1392
• Main Authors: Li, Chunhou, Li, Xican, Zeng, Jingyuan, Cai, Rongxin, Chen, Shaoman, Chen, Ban, Zhao, Xiaojun
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 20.03.2024; MDPI
• Subjects: Accuracy; Acids; Chromatography, High Pressure Liquid - methods; Citric Acid; counterfeiting recognition; Drugs, Chinese Herbal - chemistry; Gas Chromatography-Mass Spectrometry; Ginsenosides; Herbal medicine; Identification; Naodesheng Pian; quality control; Tandem Mass Spectrometry - methods; UHPLC-Q-Exactive-Orbitrap MS/MS; counterfeiting recognition; quality control; UHPLC-Q-Exactive-Orbitrap MS/MS; Naodesheng Pian
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules29061392

Tablet ( ), a traditional Chinese medicine formula for stroke treatment, is made up of five herbal medicines, i.e., , , , , and However, the current Pharmacopoeia quality-marker (Q-marker) system cannot detect possible adulteration. Our study tried to use a new strategy, i.e., standards-library-dependent ultra-high-performance liquid chromatography-quadrupole-Orbitrap mass spectrometry (UHPLC-Q-Orbitrap MS/MS) putative identification, to reconstruct the Q-marker system. Through the strategy, 30 isomers were successfully differentiated (such as 2'-hydroxygenistein, luteolin, and kaempferol; ginsenoside Rg2 and ginsenoside Rg3; ginsenoside Rf and ginsenoside Rg1). In particular, 11 compounds were unexpectedly found in , including 2'-hydroxygenistein, 7,4'-dihydroxyflavone, pectolinarigenin, 7-methoxy-4'-hydroxyisoflavone, scoparone, matrine, 3,3',4',5,6,7,8-heptamethoxyflavone, 5-hydroxyflavone, diosgenin, chloesteryl acetate, and (+)-4-cholesten-3-one. In total, 68 compounds were putatively identified and fully elucidated for their MS spectra. Subsequently, relevant compounds were further investigated using UV-vis scanning experiments, semi-quantitative analysis, and quantum chemical calculation. Finally, five adulterated Tablets were used for validation experiments. The experiment successfully detected five adulterated ones via a lower-version LC-MS analysis. On this basis, three new candidates (hydroxy safflor yellow A (HSYA), citric acid, and levistilide A), along with puerarin and notoginsenoside R1, are re-nominated as the Q-markers for LC-MS analysis. The LC-MS analysis of puerarin, notoginsenoside R1, HSYA, citric acid, and levistilide A can clearly detect adulteration regarding all five herbal medicines mentioned above. Therefore, the reconstructed Q-markers are described as a "perfect" quality control system to detect adulteration in and will offer a valuable recommendation for the Pharmacopoeia Commission.