经典名方小承气汤中化学成分的UPLC-Q-Orbitrap-MS分析

Analysis on Chemical Constituents in Xiao Chengqitang by UPLC-Q-Orbitrap-MS

目的采用超高效液相色谱-四极杆-静电场轨道阱高分辨质谱法(UPLC-Q-Orbitrap-MS)对小承气汤中的化学成分进行快速识别和鉴定。方法采用CORTECS T3色谱柱(2.1 mm×150 mm,1.6μm),以甲醇(A)-0.1%甲酸水溶液(B)作为流动相进行梯度洗脱(0~5 min,3%~21%A;5~20 min,21%~36%A;20~32 min,36%~50%A;32~42 min,50%~62%A;42~50 min,62%~85%A;50~60 min,85%~95%A),流速0.2 mL·min^(-1),柱温30℃;采用加热电喷雾离子源(HESI),正、负离子模式检测,扫描模式为Full MS/dd-MS2,扫描范围m/z100~1200,碰撞能量20,40 eV。通过与对照品比对并结合文献报道、质谱数据库信息等对化合物进行鉴别。结果从小承气汤中共鉴别了123个成分,包括33个黄酮类成分,25个蒽醌及蒽酮类成分,23个苯丙素类成分,15个鞣质类成分,10个含氮类成分及其他类化合物17个。其中,有32个成分通过与对照品比对后确认。结论利用UPLC-Q-Orbitrap-MS技术系统地阐明了小承气汤的物质基础,明确其主要化学成分黄酮类、蒽醌及蒽酮类、苯丙素类成分分别来源于枳实、大黄和厚朴,可为该复方的物质基础全面阐释和质量标准合理制定提供科学依据。

Objective To rapidly identify the chemical constituents in Xiao Chengqitang by ultra-performance liquid chromatography-quadrupole-electrostatic field orbitrap high resolution mass spectrometry(UPLC-Q-Orbitrap-MS).Method The method was established by the Waters CORTECS T3 column(2.1 mm×150 mm,1.6μm),mobile phase was methanol(A)-0.1%formic acid aqueous solution(B)for gradient elution(0-5 min,3%-21%A;5-20 min,21%-36%A;20-32 min,36%-50%A;32-42 min,50%-62%A;42-50 min,62%-85%A;50-60 min,85%-95%A),the flow rate was 0.2 mL·min^(-1),and the column temperature was 30℃.UPLC-Q-Orbitrap-MS was operated in positive and negative ion modes,the scanning range was 100^(-1)200 with mode of Full MS/dd-MS2,and the collision energies were 20,40 eV.The compounds were identified by comparing with reference substances and combining with literature reports and MS database information.Result A total of 123 components were identified in Xiao Chengqitang,including 33 flavonoids,25 anthraquinones and anthrones,23 phenylpropanoids,15 tannins,10 nitrogen-containing components and 17 other components.Among them,32 components were determined by reference substances.Conclusion The material basis of Xiao Chengqitang is flavonoids,anthraquinones and anthrones,phenylpropanoids,which is derived from Aurantii Fructus Immaturus,Rhei Radix et Rhizoma and Magnoliae Officinalis Cortex,respectively.