无梗五加根化学成分的UPLC-MS/MS分析及与细柱五加、刺五加的比较

UPLC- MS /MS analysis of the constituents in the roots of A. sessiliflorus and comparison with A. gracilistylus and A. senticosus

目的： 分析无梗五加、细柱五加和刺五加根中的化学成分并将三者进行比较。 方法： 运用UPLC-MS/MS对无梗五加、细柱五加和刺五加根中的化学成分进行一级和二级质谱分析，通过与对照品色谱峰的保留时间以及一级、二级质谱图比对鉴定其中的已知成分，并根据一级二级质谱信息推测未知成分的化学结构。色谱-质谱条件：采用Acquity UPLCTM BEH C18色谱柱（1.7 μm，100 mm×2.1 mm），以乙腈（A）-2 mmol·L^-1醋酸铵水（B）为流动相，梯度洗脱（0-15 min，8%A→25%A；15-30 min，25%A→55%A；30-40 min，55%A→80%A），流速0.15 mL·min^-1；质谱离子源为电喷雾离子化（ESI）源，正、负离子检测。 结果： 从3种五加属植物根中共鉴定了13个化合物，包括奎宁酸类成分如1，3-二咖啡酰奎宁酸、3，4-二咖啡酰奎宁酸、3，5-二咖啡酰奎宁酸；酚苷类成分如紫丁香苷；木脂素类成分如松脂醇二葡萄糖苷、无梗五加苷B、无梗五加苷D、芝麻脂素、细辛脂素、洒维宁、台湾脂素C、台湾脂素E、赛菊宁黄脂。同时推测了15个化合物，包括奎宁酸类成分如一咖啡酰奎宁酸、对香豆酰奎宁酸、阿魏酰奎宁酸；酚苷类成分如紫丁香树脂酚二葡萄糖苷、松柏苷、松柏醛葡萄糖苷、芥子醛葡萄糖苷；木脂素类成分如紫丁香苷A、紫丁香苷B、Simplexoside、Pluviatolide、3-（3，4-二甲氧基苄基）-2（3，4-亚甲基二氧苄基）丁内酯；黄酮类成分如安妥苷；香豆素类成分如刺五加苷B2、异嗪皮啶。将3种五加根中的化学成分进行比较，无梗五加根与细柱五加根成分比较相近，刺五加根中含有在无梗五加根和细柱五加根中未检测到的多种酚苷类成分如紫丁香树脂酚二葡萄糖苷、松柏苷、紫丁香苷、松柏醛葡萄糖苷、芥子醛葡萄糖苷。 结论： 无梗五加根和细柱五加根中的化学成分组成比较相似，从化学成分的角度验证了《中华本草》中对“五加皮”的来源记载，即“五加皮”为细柱五加和无梗五加植物的根皮；二者化学成分与刺五加差别较大，在药用过程中应进行区分。

Objective： To analyze and compare the constituents in the roots of Acanthopanax sessiliflorus （A.sessiliflorus）,Acanthopanax gracilistylus （A.gracilistylus） and Acanthopanax senticosus （A.senticosus）. Methods： UPLC-MS/MS was applied to verify the structure of known constituents by comparing the LC retention time and mass spectra with standard compounds and to infer the structure of unknown constituents by analyzing their Q1 scan spectra and product ion scan spectra.Chromatographic separation was achieved on an ACQUITY UPLCTM BEH C18 column （100 mm×2.1 mm,1.7 μm） with a gradient solvent system composed of acetonitrile （solvent A） and 2 mmol·L^-1 ammonium acetate-water （solvent B）;and the gradient profile was：0-15 min,8%A→25%A;15-30 min,25%A→55%A;30-40 min,55%A→80%A;with a flow rate of 0.15 mL·min^-1.The samples were analyzed with an electrospray ionization （ESI） interface set in both positive and negative ionization modes. Results： Totally 13 compounds were identified by the comparison of the LC retention time and mass spectra with standard compounds,including quinic acids such as 1,3-dicaffeoylquinic acid,3,4-dicaffeoylquinic acid and 3,5-dicaffeoylquinic acid;phenolic glycosides such as syringin;and lignans such as （＋）-pinoresinol-di-O-β-D-glucoside,（＋）-syringaresinol-di-O-β-D-glucoside,（＋）-syringaresinol-O-β-D-glucoside,taiwanin E,taiwannin C,savinin,helioxanthin,（-）-sesamin and （＋）-asrinin.15 compounds were also inferred in this study,including quinic acids such as caffeoylquinic acid,Coumaroyl acid and Feruloyl acid;phenolic glycosides such as syringin glucoside,coniferin,coniferaldehyde glucoside and sinapaldehyde glucoside;lignans such as （＋）-syringaresinoside A,（＋）-syringaresinoside B,simplexoside,pluviatolide,and 3-（3,4-dimethoxybenzyl）-2-（3,4-methylenedioxybenzyl） butyrolactone;flavonoids such as antoside;and coumarin such as eleutheroside B2and isofraxidin.The roots of A.sessiliflorus and A.gracilistylus contained similar constituents,while the roots of A.senticosus contained many phenolic glycosides such as syringin glucoside,coniferin,syringin,coniferaldehyde glucoside and sinapaldehyde glucoside,which were not detected in the roots of A.sessiliflorus and A.gracilistylus. Conclusion： The chemical composition in the roots of A.sessiliflorus and A.gracilistylus was similar,which verified that the sources of ＂cortex periplocae＂ recorded in the Chinese material medica were the root barks of both A.sessiliflorus and A.gracilistylus from the point of the chemical composition.There was big difference in chemical composition between the former two and A.senticosus,therefore the medicinal use of them should be differentiated.