Abstract In the present study, a novel database of compounds and a screening method based on ultra-high performance liquid chromatography coupled to high resolution orbitrap mass spectrometry (UHPLC-Orbitrap HRMS) were developed. The method was applied to the rapid screening and identification of targeted and non-targeted antitussive adulterants in herbal medicines. The database includes retention time, exact mass, fragments, isotopic pattern and MS2 spectra library of the target compounds and provides automated search and identification of the target adulterants with merely a single injection. On the other hand, the full MS scan and MS2 HRMS data allow the identification of non-targeted compounds in samples with the assisted analysis of XCalibur4.0, MassFrontier7.0 and TraceFinder3.3 software and Chemspider database. The established HRMS method also possesses excellent quantitative capacity. All LOD values were in the range of 0.006 to 0.03 μg/g, while the values of all determination coefficients were higher than 0.9992 for all analytes. The intra– and inter–day accuracies were in the range of 92.4 to 108.3%, while the intra– and inter–day precision ranged from 2.6% to 8.7%. The screening database and method were used to detect antitussive adulterants in herbal medicines. Among 87 batches of herbal medicines which claimed “all-natural” and function of antitussive, 12 batches of samples were found as positive. The detected antitussive adulterants include target adulterants such as theophylline, sulfamethoxazole, prednisone acetate, chlorphenamine, pentoxyverine and non-targeted adulterants such as trimethoprim, dioxopromethazine, aspirin, diclofenac and cephalexin, with levels in the range of 0.271 ∼ 135.21 mg/g. Our work demonstrates that this novel orbitrap HRMS screening database for adulterants is a very promising and powerful tool for routine screening of illegal adulterated antitussives in herbal medicines in order to ensure the drug safety and public health.

中文翻译：

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通过 Q-Orbitrap HRMS 和筛选数据库快速筛选和识别草药中的靶向或非靶向镇咳掺杂物

摘要 在本研究中，基于超高效液相色谱与高分辨率轨道阱质谱联用 (UHPLC-Orbitrap HRMS) 开发了一种新的化合物数据库和筛选方法。该方法用于中草药中靶向和非靶向镇咳掺杂物的快速筛选和鉴定。该数据库包括目标化合物的保留时间、精确质量、碎片、同位素模式和 MS2 谱库，并且只需一次进样即可自动搜索和识别目标掺杂物。另一方面，完整的 MS 扫描和 MS2 HRMS 数据允许通过 XCalibur4.0、MassFrontier7.0 和 TraceFinder3.3 软件和 Chemspider 数据库的辅助分析来识别样品中的非目标化合物。已建立的 HRMS 方法还具有出色的定量能力。所有 LOD 值均在 0.006 至 0.03 μg/g 范围内，而所有分析物的所有测定系数值均高于 0.9992。日内和日间准确度在 92.4% 至 108.3% 的范围内，而日内和日间精度在 2.6% 至 8.7% 之间。筛选数据库和方法用于检测草药中的镇咳掺杂物。在87批号称“纯天然”、具有镇咳作用的中药材中，有12批样品呈阳性。检测到的镇咳掺杂物包括茶碱、磺胺甲恶唑、醋酸泼尼松、扑尔敏、戊氧维林等目标掺杂物和甲氧苄啶、二氧异丙嗪、阿司匹林、双氯芬酸和头孢氨苄，浓度范围为 0.271 ∼ 135.21 mg/g。我们的工作表明，这种新型的 Orbitrap HRMS 掺杂物筛查数据库是一种非常有前途和强大的工具，用于常规筛查草药中的非法掺假镇咳药，以确保药物安全和公众健康。