目的 利用UPLC-Q-Exactive四极杆-静电场轨道阱高分辨质谱仪联用技术，快速识别与鉴定民族药小大黄Rheum pumilum的化学成分。方法 以100%甲醇作为提取液制备供试液，采用ACQUITY UPLC BEH C₁₈色谱柱（100 mm×2.1 mm，1.7 μm）分离，以甲醇-0.1%甲酸水溶液为流动相进行梯度洗脱，质谱采用正负离子监测模式、采用全扫描及自动触发二级质谱扫描的功能，对小大黄化学成分进行快速识别及鉴定。结果 通过高分辨数据共鉴定了34个化学成分，包括蒽醌类11个，酚/酰基糖苷类4个、鞣质前体及鞣质类3个、二苯乙烯类9个、黄酮类2个、萘苷类3个、苯丁酮类2个，其中7个成分经与对照品比对而准确鉴定，28个化学成分为该植物中首次报道。结论 使用UPLC-Q-Exactive四级杆-静电场轨道阱高分辨质谱技术，建立高分辨质谱数据库，总结对照品裂解规律，使用少量对照品快速分析鉴定出多个小大黄化学成分，有利于明确小大黄的物质基础，表明该技术在中草药化学成分分析及鉴定方面具有良好的应用前景。

Objective An ultra-high performance liquid chromatography coupled with hybrid quadrupole-orbit trap mass spectrometry (UPLC-quadrupole-orbit trap MS) method was developed and used to rapidly recognize and identify the chemical constituents in the roots of Rheum pumilum. Methods With 100% methanol as extract preparation for solution, the extract was separated on an ACQUITY UPLC BEH C₁₈ column (100 mm × 2.1 mm, 1.7 μm) and eluted with a gradient of methanol-water containing 0.1% formic acid. Mass spectrometry using positive and negative ion monitoring mode. The constituents in the roots of R. pumilum were rapidly recognized and identified by HRMS in the negative ion mode using both full scan and automatic triggering of the function of the two stage mass spectrometry scanning. Results A total of 34 compounds, including 11 anthraquinones, 4 acyl indicans, 3 tannin precursor and tannins, 9 toluylenes, 2 flavonoids, 3 nai glycosides, and 2 benzyl butyl ketones were identified. Among them, 7 compounds were unambiguously identified by comparing with the reference standards and. 28 chemical compositions were reported for the first time in the roots of R. pumilum. Conclusion The high resolution mass spectrometry database has been established by UPLC-quadrupole-orbit trap MS and the fragmentation pattern of reference substances is summarized. Many constituents from the roots of R. pumilum could be rapidly analyzed and identified. This study demonstrates that the UPLC-quadrupole-orbit trap MS is a powerful, rapid, and accurate tool in the structural identification of unknown constituents in Chinese herbal medicine with a good application prospects.

国家留学基金委青年骨干教师研修项目（201500850007）；西南民族大学研究生创新型科研项目（CX2015SZ034）