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采用超高效液相色谱-串联质谱法分析 中的类黄酮。

Analysis of Flavonoids in by Ultra-Performance Liquid Chromatography with Tandem Mass Spectrometry.

机构信息

Hainan Provincial Key Laboratory of Resources Conservation and Development of Southern Medicine, Hainan Branch of the Institute of Medicinal Plant Development, Chinese Academy of Medical Sciences & Peking Union Medical College, Haikou 570311, China.

School of Life Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, China.

出版信息

Molecules. 2020 Jan 17;25(2):389. doi: 10.3390/molecules25020389.

Abstract

, a traditional Chinese medicine, has been used to treat cardio- and cerebrovascular diseases in China for thousands of years. Flavonoids are major active compounds in . In this paper, a rapid and sensitive ultra-high performance liquid chromatography-triple quadrupole mass spectrometry method was developed and validated for simultaneous determination of 17 flavonoids in . Quantification was performed by multiple reaction monitoring using electrospray ionization in negative ion mode. Under the optimum conditions, calibration curves for the 17 analytes displayed good linearity ( > 0.9980). The intra- and inter-day precisions (relative standard deviations) were lower than 5.0%. The limit of quantitation ranged from 0.256 to 18.840 ng/mL. The mean recovery range at three spiked concentrations was 94.18-101.97%. The validated approach was successfully applied to 18 samples of . Large variation was observed for the contents of the 17 analytes. Sativanone and 3'--methylviolanone were the dominant compounds. The fragmentation behaviors of six flavonoids were investigated using UPLC with quadrupole time-of-flight tandem mass spectrometry. In negative ion electrospray ionization mass spectrometry, all the flavonoids yielded prominent [M - H] ions. Fragments for losses of CH, CO, and CO were observed in the mass spectra. Formononetin, liquiritigenin, isoliquiritigenin, sativanone, and alpinetin underwent retro-Diels-Alder fragmentations. The proposed method will be helpful for quality control of .

摘要

作为一种传统中药,已在中国被用于治疗心脑血管疾病数千余年。类黄酮是 的主要活性化合物。在本文中,建立并验证了一种快速灵敏的超高效液相色谱-三重四极杆质谱法,用于 中 17 种类黄酮的同时测定。采用电喷雾负离子模式下的多反应监测进行定量分析。在最佳条件下,17 种分析物的校准曲线均具有良好的线性(>0.9980)。日内和日间精密度(相对标准偏差)均低于 5.0%。定量限范围为 0.256-18.840ng/mL。在三个加标浓度下,平均回收率范围为 94.18-101.97%。该方法已成功应用于 18 个 样品的分析。在 17 种类黄酮的含量方面观察到了很大的差异。萨替宁酮和 3'--甲基香草酮为主要化合物。采用超高效液相色谱-四极杆飞行时间串联质谱法研究了六种类黄酮的裂解行为。在负离子电喷雾电离质谱中,所有类黄酮均产生明显的[M-H]离子。在质谱中观察到 CH、CO 和 CO 的丢失碎片。芒柄花素、甘草素、异甘草素、萨替宁酮和川陈皮素发生逆狄尔斯-阿尔德裂解。所提出的方法将有助于 的质量控制。

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