目的 应用固相萃取结合超高效液相色谱-线性离子阱-静电场轨道质谱（UHPLC-LTQ-Orbitrap MS）技术对黄精发酵前后的化学成分进行分析鉴定。方法 采用Waters HSS T3（100 mm×2.1 mm，1.7 μm）色谱柱，以0.1%甲酸水溶液和的乙腈为流动相梯度洗脱，体积流量0.3 mL/min，在电喷雾正离子模式下进行检测，四级杆飞行时间串联质谱法对各主要色谱峰进行归属。结果 根据所获得的精确相对分子质量，同时结合色谱保留行为、质谱裂解规律、特征碎片离子、对照品比对以及相关文献报道，共鉴定发酵前后黄精中的69个化学成分，包括57个甾体皂苷类成分、5个黄酮类成分、4个三萜皂苷类成分、2个生物碱类及1个有机酸类成分。其中，从发酵前黄精提取液中鉴定了62个化学成分，从发酵后黄精提取液中鉴定了18个化学成分。结论 发酵对黄精中的化学成分影响很大，如成分异构化、原生苷种类以及含量减少、次生苷或苷元含量的增多等，可为黄精的进一步开发利用提供科学依据。

Objective To analyze and identify the chemical constituents in aqueous extracts and fermentation broth from Polygonatum sibiricum by ultra performance liquid chromatography-linear ion trap-electrostatic field orbital mass spectrometry (UHPLC-LTQ-Orbitrap MS) combined with solid phase extraction. Methods The separation was performed on Waters HSS T3 (100 mm×2.1 mm, 1.7 μm) with acetonitrile and 0.1% formic acid solution as the mobile phase in gradient elution. The flow rate was 0.3 mL/min. The detection was carried out in electrospray positive ion mode, and the main peaks were assigned by quadrupole time-of-flight mass spectrometry. Results According to the obtained accurate molecular weight, combined with chromatographic retention behavior, mass spectrometry cleavage, characteristic fragment ions, reference comparison, and related literature reports, a total of 69 chemical components were identified in aqueous extracts and fermentation broth from P. sibiricum, including 57 steroidal saponins, five flavonoid components, four triterpenoid saponins, two alkaloids, and one organic acid component. Among them, 62 chemical components were identified from the aqueous extracts, and 18 chemical components were identified from the fermentation broth of P. sibiricum. Conclusion The results showed that fermentation has a great influence on the chemical components of P. sibiricum, including the isomerization of components, types and content reduction of primary glycosides and the concentration of components changed of secondary glycosides in different degrees, which provides the necessary scientific basis for the further development of P. sibiricum.

2018年北京中医药大学杰出青年人才项目（2018-JYB-XJQ008）；2017年北京市科技新星与领军人才培养专项计划（Z171100001117029）