反相-混合柱色谱串联MS法探索中药半夏的化学成分  

Study on the chemical composition of traditional Chinese medicine Pinellia ternate by C18-mixed-stationary phase column LC-MS

作　　者：徐文英[1] 刘春生[1] 冯孟鑫 马恺悦 高山山[1] 侯文珍[1] 王佳宇[1] 马长华[1] 

机构地区：[1]北京中医药大学中药学院,北京100102

出　　处：《西北药学杂志》2015年第4期354-357,共4页Northwest Pharmaceutical Journal

基　　金：北京市自然科学基金项目(编号:7142101)

摘　　要：目的对中药半夏中在C18色谱柱上保留较弱的化学成分进行分离与鉴定。方法首先采用Waters X-Bridge C18色谱柱(150mm×4.6mm,5μm)对半夏药材酸水提取液进行分离,然后对半夏提取液中在C18柱上保留较弱的成分采用Tech Mate TX色谱柱(120A,150mm×2.0mm,5μm)(SCX与反相C18混合填料色谱柱)进行进一步分离分析,最后采用LC-MS对所分离成分进行鉴定,ESI正离子模式扫描分析。结果根据正离子模式下获得的各色谱峰的质谱数据,共检测到13个主要的化学成分,其中3个通过与文献对照或根据质谱裂解规律得到了确认,分别为:缬氨酸,腺嘌呤,精氨酸;化合物1,2,4,5,7,8和13推测为:5-羟甲基糠醛,6 H-purin-6-1,2-amino-1,9-dihydro-8-(1-naphthalenylamino),环-(缬氨酸-酪氨酸),环-(亮氨酸-酪氨酸),亮氨酸-异亮氨酸,(-)-pohakulin pohakuline,N-(1-(苯基乙酰基)-L-脯氨酰)甘氨酸乙酯,化合物9推测为某种环肽;化合物10和11由于缺乏相关对照品和相关文献报道,其结构有待进一步分析鉴定。结论在C18柱上死时间内流出而不能很好分离的物质,在混合填料柱上得到了进一步分离,这说明在某种程度上,采用单一固定相不能很好分离的某些化合物可以采用混合固定相色谱柱达到进一步分离,尤其是在对复杂体系样品的分离及鉴定过程中,混合固定相色谱柱将具有良好的应用前景。Objective To separate and identify the chemical compositions of Pinellia ternate which is slightly reserved on the C18 column.Methods Firstly a Waters X-Bridge C18 column was used to separate the acidic water extract of Pinellia ternate,and then the Tech Mate^TX column（120A,150 mm×2.0 mm,5μm）（SCX-C18 mixed stationary phase column）was used to separate the components that slightly retained on the C18 column,and finally the components that slightly retained on the C18 column were separated and identified by LC-MS-ESI in a positive ion mode.Results According to the positive ion mode available mass spectral data for each chromatographic peak,13 major chemical constituents were detected,3of which were confirmed by literature or under the control of MS fragmentation mechanism.They were adenine,valine,and arginine.Compounds 1,2,4,5,7,8 and 13 were：5-hydroxymethyl furfural,6 H-purin-6-1,2-amino-1,9-dihydro-8-（1-naphthalenylamino）,ring-（Val Tyr）,cyclo（leu-tyr）,leucine-isoleucine,（-）-pohakulinpohakuline,and N-（1-（phenylacetyl）-L-prolyl）glycine ethyl ester.Compound 9 was presumed to be a cyclic peptide;due to the lack of control and related literatures,the structure of compounds 10 and 11 need to be identified for further analysis.Conclusion The substances which were flowed out in the dead time on the C18 column can be separated on the mixed-stationary phase column.The mixed-stationary phase will has a good application prospects.

关 键 词：半夏 混合固定相 高分辨质谱 

分 类 号：R284[医药卫生—中药学]