Key Laboratory of Ethnomedicine (Minzu University of China) Ministry of Education, School of Pharmacy, Minzu University of China, Beijing 100081, China; Modern Research Center for Traditional Chinese Medicine, School of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing 100029, China.
Shandong Institute for Food and Drug Control, Jinan 250101, China.
J Chromatogr B Analyt Technol Biomed Life Sci. 2021 Jun 30;1176:122735. doi: 10.1016/j.jchromb.2021.122735. Epub 2021 May 12.
In comparison of liquid chromatography, direct infusion is a superior choice to achieve high-throughput measurements. The specificity and selectivity of tandem mass spectrometry (MS/MS) actually result in a so-called MS separation potential when chemical characterization of herbal medicines. Here, a MS/MS program was introduced to promote DI-MS/MS to be an eligible tool for shotgun chemome characterization of Artemisia rupestris L. that is currently drawing worldwide interests because of the promising antiviral activity. After MS spectral acquisition for the crude extract, the gas phase fractionation concept enabled the precursor ion cohort sequentially entered the collision cell with a stepped unit mass window (step-size as 1 Da) to generate MS spectra, thus generating a unique property integrating the advantages of both data-dependent and data-independent acquisition manners. Even though being free of chromatographic separation, spectrometric separations were accomplished for by MS/MS program unless the components shared identical nominal molecular weights. Extensive efforts such as the correlations of MS signals with MS spectra, structural annotations of fragment ion species, information retrieval in some accessible databases, and referring to the literature data, were devoted for chemical characterization, and as a result, 44 compounds, in total, were structurally identified from 50% aqueous methanol exact of A. rupestris, including 8 caffeoyl quinic acid derivatives, 13 flavonoids, 15 monomeric and dimeric sesquiterpenoids, 4 fatty acids, 2 penylpropanoids, along with 2 other compounds. However, isomers were assigned as an isomeric mixture because their precursor ions always co-existed in a single mass window. Above all, DI-MS/MS provides an alternative tool for chemome characterization of herbal medicines, in particular when the great measurement workload for a large sample cohort, attributing to the high-throughput advantage.
与液相色谱相比，直接进样是实现高通量测量的更佳选择。串联质谱（MS/MS）的特异性和选择性实际上在草药的化学特征分析中产生了所谓的 MS 分离潜力。在这里，引入了一个 MS/MS 程序，以促进 DI-MS/MS 成为 Artemisia rupestris L. 的 shotgun 化学特征分析的一种合格工具，由于其有希望的抗病毒活性，目前引起了全球关注。在对粗提物进行 MS 光谱采集后，气相分馏概念使前体离子群依次以 1 Da 的步进单位质量窗口进入碰撞池，以生成 MS 光谱，从而生成一种独特的特性，整合了数据依赖和独立采集方式的优势。即使没有色谱分离，通过 MS/MS 程序也可以实现光谱分离，除非成分具有相同的名义分子量。为了进行化学特征分析，我们进行了广泛的努力，例如将 MS 信号与 MS 光谱相关联、对碎片离子种类进行结构注释、在一些可访问的数据库中进行信息检索，并参考文献数据，共从 50%甲醇水溶液的 A. rupestris 中鉴定出 44 种化合物，包括 8 种咖啡酰奎宁酸衍生物、13 种类黄酮、15 种单体和二聚倍半萜、4 种脂肪酸、2 种苯丙素类化合物以及 2 种其他化合物。然而，由于它们的前体离子总是在单个质量窗口中共存，因此将异构体分配为异构体混合物。总之，DI-MS/MS 为草药的化学特征分析提供了一种替代工具，特别是在对大量样本进行高通量测量时，这归因于其高通量的优势。
