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采用超高效液相色谱-串联质谱法结合化学计量学对多产地茜草属植物中醌类物质的定性定量分析。

Qualitative and quantitative analyses of quinones in multi-origin Rubia species by ultra-performance liquid chromatography-tandem mass spectrometry combined with chemometrics.

机构信息

Department of TCMs Pharmaceuticals, School of Traditional Chinese Pharmacy, China Pharmaceutical University, Nanjing 211198, People's Republic of China.

Department of TCMs Pharmaceuticals, School of Traditional Chinese Pharmacy, China Pharmaceutical University, Nanjing 211198, People's Republic of China.

出版信息

J Pharm Biomed Anal. 2020 Sep 10;189:113471. doi: 10.1016/j.jpba.2020.113471. Epub 2020 Jul 13.

DOI:10.1016/j.jpba.2020.113471
PMID:32731129
Abstract

Rubia species are one of the important multi-origin phytomedicines having both economical and medicinal values in many countries. Quinones are the predominant bioactive constituents of these species. Therefore, accurate analysis of these quinones is critical to quality control, clinical, and commercial applications of Rubia species. In this study, a sensitive and efficient ultra-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry (UPLC-QqQ-MS/MS) method in positive and negative multiple reaction monitor (+/-MRM) modes was firstly developed for the characterization of 45 quinones and the quantification of 24 quinones from Rubia plants. The chromatographic separation was achieved on a Waters ACQUITY UPLC® BEH C column by using a gradient elution with a mobile phase consisting of 0.1 % formic acid in water and acetonitrile. The results indicated that quinones in multi-origin Rubia samples were different, but 10 quinones existed in all samples. R. cordifolia, which is a unique official medicinal material in Chinese Pharmacopeia, contained the most number of quinones among all the Rubia species. R. podantha and R. sylvatica had the next highest number of quinones, implying that these species could be used as alternatives for R. cordifolia. Chemometric approaches were applied to evaluate the chemical relationship between the Rubia samples based on the constituent quinones. In this study, a UPLC-QqQ-MS/MS method in the MRM mode has been developed for the analysis of Rubia species-derived quinones, which not only contributes to quality control and discrimination of Rubia species, but also suggests the potential of these species in clinical and commercial applications.

摘要

茜草属植物是一类具有重要经济和药用价值的多源性植物药材,在许多国家都有应用。醌类化合物是这些植物的主要生物活性成分。因此,准确分析这些醌类化合物对于茜草属植物的质量控制、临床应用和商业应用至关重要。本研究首次建立了一种灵敏、高效的超高效液相色谱-串联三重四极杆质谱法(UPLC-QqQ-MS/MS),采用正负多重反应监测(+/-MRM)模式,用于鉴定茜草属植物中的 45 种醌类化合物,并对 24 种醌类化合物进行定量分析。色谱分离在 Waters ACQUITY UPLC® BEH C 柱上进行,采用梯度洗脱,流动相由 0.1%甲酸水溶液和乙腈组成。结果表明,多源性茜草样品中的醌类化合物存在差异,但 10 种醌类化合物存在于所有样品中。在中国药典中,茜草是一种独特的官方药用植物,其所含的醌类化合物种类最多。茜草和云南茜草次之,这表明这两种植物可以作为茜草的替代品。化学计量学方法被应用于基于成分醌类化合物来评价茜草样品之间的化学关系。本研究建立了一种 UPLC-QqQ-MS/MS 方法,用于分析茜草属植物来源的醌类化合物,不仅有助于茜草属植物的质量控制和鉴别,还为这些植物在临床和商业应用中的潜在应用提供了依据。

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