基于UPLC-Q-TOF MS分析加工炮制对玄参化学成分的影响

为了全面阐明玄参加工工艺对其化学成分的影响,采用UPLC-Q-TOF MS技术对烘干玄参和传统加工玄参的化学成分进行分析比较,并运用主成分分析法(PCA)和正交偏最小二乘辨别分析法(OPLS-DA)进行数据统计,寻找差异性成分,同时依据一级质谱精确质荷比和二级质谱碎片信息进行成分解析。结果表明:与烘干玄参相比,传统加工玄参中共有26种成分的含量变化显著,实验鉴定出了其中的15种成分,包括9种环烯醚萜类化合物和6种苯丙素类化合物;含量降低的成分有桃叶珊瑚苷、6-O-甲基梓醇、哈巴俄苷、8-O-香豆酰基哈巴俄苷、8-O-阿魏酰基哈巴俄苷、阿格托苷、异阿格托苷、安格洛苷C和scrophuloside B1,其中scrophuloside B1为玄参中首次发现的成分;含量增加的成分有哈巴苷、哈巴俄苷同分异构体、6″-O-α-D-半乳糖哈巴俄苷、6-O-α-D-半乳糖哈巴俄苷、斩龙剑苷A和肉桂酸。本工作对研究玄参加工炮制机制有重要意义,同时可为阐明玄参药效的物质基础提供依据。

Changes of Chemical Constituents in Scrophulariae Radix During Processing Based on UPLC-Q-TOF MS

In order to clarify the influence of the traditional processing on the chemical constitution ofScrophulariae Radix, the UPLC-Q-TOF MS method was used to analyze the dried and processed Scrophulariae Radix. Data were processed by principal component analysis (PCA) and orthogonal partial least squared discriminant analysis (OPLS-DA) to find the difference between dried and processedScrophulariae Radix. The accurate m/z values of Q-TOF MS and Q-TOF MS/MS fragments were applied to constitution identification. The results show that a total of 26 constituents have significant differences between dried and processedScrophulariae Radix. Fifteen constituents are identified, including 9 iridoid glycosidesand 6 phenylpropanoid glycosides. Compared with the driedScrophulariae Radix, the contents of aucubin, 6-O-methylcatapol, harpagoside, 8-O-cumaroylharpagide, 8-O-feruloylharpagide, acteoside, isoacteoside, angoroside C and scrophuloside B₁ in processed Scrophulariae Radixwere are decreasing. The contents of harpagide, harp agoside isomer, 6″-O-α-D-galactopyranosylharp agoside, 6-O-α-D-galactopyranosylharp agoside, sibirioside A and cinnamic acid are increasing. InScrophulariae Radix, scrophuloside B₁ is detected for the first time. The UPLC/Q-TOF-MS method proves to have a high sensitivity and the result isaccurate and reliable. The method could fully reflect the changes of multiple chemical constituents in the course of processing and lay a good foundation for the further study of processing mechanism of traditional Chinese medicine.