通过超高效液相色谱-Q-轨道rap-MS/MS 对紫花地丁中的 36 种化合物进行鉴定和半定量,并提出药典防伪质量标记的建议

IF 1.2 4区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Chromatographia Pub Date : 2024-07-04 DOI:10.1007/s10337-024-04348-6
Shaoman Chen, Xican Li, Chunhou Li, Rongxin Cai, Ban Chen, Guihua Jiang, Yongbai Liang, Xu Chen
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引用次数: 0

摘要

紫花地丁是一种常见的中药材。现行的《中国药典》(ChP)将牧野紫草(Viola yedoensis Makino)定义为唯一的植物来源,并将埃斯奎林(Esculetin)定义为唯一的质量标记(Q-marker)。然而,一些假药中也含有埃斯库莱廷。这意味着目前的 ChP 标准实际上无法识别假冒的 V. yedoensis。因此,该研究利用超高效液相色谱-四极杆-奥比阱串联质谱(UHPLC-Q-Orbitrap-MS/MS)分析技术创建了一个专门的质谱库。通过文库比对,成功从 V. yedoensis 中鉴定出 36 种化合物,特别是成功区分出四种异构体,即 vitexin 与 isovitexin、schaftoside 与 isoschaftoside。随后的超高效液相色谱-Q-Orbitrap-MS/MS半定量分析表明,36 种化合物的化学含量从 0.001% 到 1.958% 不等,其中老 Q 标志物 esculetin 的含量较高(0.484 ± 0.028%)。根据相关原理,建议将黄酮类化合物木犀草素作为新的补充 Q 标记。该建议为识别 V. yedoensis 的七种掺假(或伪造)提供了初步证据。
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Identification and Semi-quantification of 36 Compounds from Violae herba (Zihuadiding) via UHPLC-Q-Orbitrap-MS/MS as Well as Proposal of Anti-counterfeiting Quality-Marker for Pharmacopeia

Violae herba (Zihuadiding) is a common Chinese herbal medicine. The current Chinese Pharmacopeia (ChP) defines Viola yedoensis Makino as the sole plant origin and esculetin as its sole quality-marker (Q-marker). Esculetin, however, occurs in some counterfeits as well. This implies that current ChP criterion actually cannot recognize the counterfeits of V. yedoensis. The study thus created a specialized MS library using ultra-high-performance liquid chromatography with quadrupole-orbitrap tandem mass spectrometry (UHPLC-Q-Orbitrap-MS/MS) analysis. Through library-comparison, 36 compounds were putatively identified from V. yedoensis; especially, four isomers were successfully distinguished, that is, vitexin vs isovitexin and schaftoside vs isoschaftoside. The subsequent UHPLC-Q-Orbitrap-MS/MS semi-quantification suggested that the chemical contents of 36 compounds varied from 0.001 to 1.958% and the old Q-marker esculetin had high content (0.484 ± 0.028%). According to the relevant principles, flavonoid luteolin was proposed as the new and additional Q-marker. The proposal offers a preliminary evidence to recognize seven adulterations (or counterfeits) of V. yedoensis.

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来源期刊
Chromatographia
Chromatographia 化学-分析化学
CiteScore
3.40
自引率
5.90%
发文量
103
审稿时长
2.2 months
期刊介绍: Separation sciences, in all their various forms such as chromatography, field-flow fractionation, and electrophoresis, provide some of the most powerful techniques in analytical chemistry and are applied within a number of important application areas, including archaeology, biotechnology, clinical, environmental, food, medical, petroleum, pharmaceutical, polymer and biopolymer research. Beyond serving analytical purposes, separation techniques are also used for preparative and process-scale applications. The scope and power of separation sciences is significantly extended by combination with spectroscopic detection methods (e.g., laser-based approaches, nuclear-magnetic resonance, Raman, chemiluminescence) and particularly, mass spectrometry, to create hyphenated techniques. In addition to exciting new developments in chromatography, such as ultra high-pressure systems, multidimensional separations, and high-temperature approaches, there have also been great advances in hybrid methods combining chromatography and electro-based separations, especially on the micro- and nanoscale. Integrated biological procedures (e.g., enzymatic, immunological, receptor-based assays) can also be part of the overall analytical process.
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