基于UPLC-Q TOF MS联合多元统计分析及分子网络的百合及卷丹化学成分差异性研究  

Multivariate statistical analysis combined with molecular networking to analysis the components between the bulbus of Lilium lancifolium Thunb.and L.brownii F.E.Brown var.viridulum Baker

作　　者：付钰[1,2] 王碧莹 张欣亚 荣晓庆 陈随清 FU Yu;WANG Bi-ying;ZHANG Xin-ya;RONG Xiao-qing;CHEN Sui-qing(School of Pharmacy,Henan University of Chinese Medicine,Zhengzhou 450046,China;Henan Lingrui Pharmaceutical Company,Xinyang 465550,China;Collaborative Innovation Center for Respiratory Disease Diagnosis and Treatment&Chinese Medicine Development of Henan Province,Henan University of Chinese Medicine,Zhengzhou 450046,China)

机构地区：[1]河南中医药大学药学院,郑州450046 [2]河南羚锐制药股份有限公司,信阳465550 [3]河南中医药大学呼吸病协同创新中心,郑州450046

出　　处：《药物分析杂志》2024年第10期1699-1712,共14页Chinese Journal of Pharmaceutical Analysis

基　　金：河南省高等学校重点科研项目(24A360004);河南省中医药科学研究专项课题重大专项(2022ZYZD18)。

摘　　要：目的:采用超高效液相色谱串联四极杆飞行时间质谱(UPLC-Q TOF MS)技术,联合多元统计分析和分子网络分析,解析百合及卷丹化学成分的差异性。方法:采用Agilent poroshell 120 EC-C_(18)(100 mm×2.1 mm,2.7μm)色谱柱,以乙腈(A)-0.01%甲酸水溶液(B)为流动相,流速0.3 mL·min^(-1),柱温30℃,进样量1μL;电喷雾离子源,正、负离子模式检测,扫描范围m/z 80~1100,分析新鲜百合及卷丹样品。数据采集后进行化学轮廓分析,首先运用主成分分析(PCA)比较二者化学轮廓差异性,发现百合及卷丹在化学成分上存在明显差异。进而通过正交偏最小二乘法(OPLS-DA)结合单因素分析对百合和卷丹的差异化合物群进行筛选。最后,以差异化合物群中各成分MS/MS碎片信息为依据,通过GNPS平台构建分子网络,并通过Cytoscape 3.7.2软件筛选结构相似的分子簇并绘制可视化网络图。通过对照品比对、网络数据库检索等方式鉴定各分子簇“种子”成分,以“种子”成分为线索解析不同来源百合差异成分群结构组成。结果:百合和卷丹主要在酚酸甘油酯、生物碱和皂苷成分群中存在差异,其中生物碱类为百合的优势成分群,而甾体皂苷类为卷丹的优势成分群。并通过分子网络在二者的差异成分群中鉴定出31个化合物,其中包括酚酸甘油酯类18个、生物碱类7个及皂苷类成分6个。结论:百合及卷丹在化学成分上存在较大差异,差异成分对于药材的品质,在复方中的功效和含复方临床疗效之间的关系还需进一步研究。本研究为百合的合理利用及精准开发提供数据参考,也为中药化学成分表征及快速鉴别提供借鉴。Objective:To explore the difference of chemical composition between the bulbus of Lilium lancifoliumThunb.and L.brownii F.E.Brown var.viridulum Baker,the chemical profile of Lilii Bulbus was acquired by ultra-high performance liquid chromatography with quadrupole-time of flight mass spectrometry(UPLC-Q TOF MS),then the components of all samples was analyzed by chemometrics combined with molecular networking.Methods:The Agilent poroshell 120 EC-C_(18)column(100 mm×2.1 mm,2.7μm)was adopt,and the mobile phase was acetonitrile-0.1%formic acid aqueous solution with gradient elution.The flow rate was 0.3 mL·min^(-1),the column temperature was 30℃and the injection volume was 1μL.The mass spectra were acquired in the positive and negative modes in the mass range of m/z 80-1100.Principal component analysis(PCA),partial least squares-discriminant analysis(OPLS-DA)and single factor analysis were used for screening the differential components.Then GNPS molecular network was created according to the similarity of MS/MS fragmentation modes.Cytoscape 3.7.2 software was used to screen molecular clusters with similar structures.Results:Phenolic acid glycerides,alkaloids and steroid saponins were screened as the differential components groups.Among these components,the bulbus of Lilium lancifolium Thunb.was rich in steroid saponins,while the bulbus of L.brownii F.E.Brown var.viridulum Baker was rich in alkaloids.Besides,31 components,including 18 phenolic acid glycerides,7 alkaloids and 6 steroid saponins were identified in the three differential components groups.Conclusion:This method can provide reference data for the quality control and pharmacodynamic substances of Lilii Bulbus,and provide reference for the rapid qualitative analysis of chemical components of traditional Chinese medicine.

关 键 词：百合 卷丹 液质联用 多元统计 分子网络 成分差异 

分 类 号：R917[医药卫生—药物分析学]