摘要
该研究系统比较生黄连、萸黄连及炮制辅料吴茱萸汁的挥发性成分差异,筛选萸黄连特征挥发性标志物,并阐明其“辛辣”气味的物质基础。采用顶空-气相色谱-离子迁移色谱(HS-GC-IMS)分析生黄连、萸黄连及吴茱萸汁样品中的挥发性成分,根据美国国家标准与技术研究院(NIST)2020数据库与IMS数据库对挥发性成分进行鉴定;使用VOCal 04.07软件和Gal-lery Plot插件对3种样品进行指纹图谱对比;使用SIMCA 14.1软件对3种样品进行化学计量学分析,以变量投影重要性值(VIP)>1.0,P<0.05,差异倍数(FC)>1.2或<0.83的变量作为萸黄连的特征挥发性标志物,并结合相对气味活度值(ROAV)分析3种样品的气味组成情况。HS-GC-IMS共检测到161种挥发性成分,鉴定出酯类、酮类、醛类等12类共124种化合物。其中酯类、酮类、醛类、萜类和醇类化合物是生黄连、萸黄连、吴茱萸汁三者共有的主要的挥发性成分类别,炮制后萸黄连样品中酯类、酮类、醛类、萜类、醇类、有机酸类、醚类、酚类8类成分相对峰强下降,而杂环类、硫化物类、烯烃类、芳香烃类4类成分相对峰强升高,这可能与辅料吴茱萸汁的引入有关。指纹图谱和化学计量学显示,生黄连、萸黄连和吴茱萸汁三者样品间存在明显差异,各样品可明显区分聚类。分析发现,1-戊烯-3-酮、正戊醛二聚体、2-丁基呋喃、硫氰酸甲酯等辛辣气味相关成分在萸黄连中ROAV明显提升,且与吴茱萸汁的引入密切相关。萸黄连的炮制通过引入吴茱萸汁中的化学成分并促进化学反应,明显改变了挥发性成分组成,增强了“辛辣”气味特征。该研究为萸黄连饮片的炮制科学内涵研究提供了参考。
This study aims to systematically compare the volatile components of raw Coptidis Rhizoma,Euodia rutaecarpa-processed Coptidis Rhizoma,and E.rutaecarpa juice,identify characteristic volatile markers of E.rutaecarpa-processed Coptidis Rhizoma,and elucidate the chemical basis of its"pungent"odor.The volatile components were analyzed by using headspace-gas chromatography-ion mobility spectrometry(HS-GC-IMS)and identified via the National Institute of Standards and Technology(NIST)2020 and IMS databases.Chemical fingerprints of the three samples were compared by using VOCal 04.07 software and the Gallery Plot plugin.Chemometric analysis of the three samples was performed by SIMCA 14.1 software,with variables of variable importance in projection(VIP)>1.0,P<0.05,and fold change(FC)>1.2 or<0.83 as characteristic volatile markers of E.rutaecarpa-processed Coptidis Rhizoma.Relative odor activity values(ROAV)were calculated to evaluate odor contributions of the three samples.A total of 161 volatile components were detected by HS-GC-IMS,with 124 identified,including esters,ketones,aldehydes,and 12 other chemical categories.Common major volatile classes in raw Coptidis Rhizoma,E.rutaecarpa-processed Coptidis Rhizoma,and E.rutaecarpa juice were esters,ketones,aldehydes,terpenes,and alcohols.After processing,E.rutaecarpa-processed Coptidis Rhizoma exhibited reduced relative peak intensities in eight categories(esters,ketones,aldehydes,terpenes,alcohols,organic acids,ethers,and phenols)and increased intensities in four categories(heterocyclic compounds,sulfur-containing compounds,alkenes,and aromatic hydrocarbons),likely due to the addition of E.rutaecarpa juice.Chemometric analysis and fingerprinting showed distinct differences among the three samples,with the clustering of each sample differentiated clearly.ROAV analysis revealed significant increases in pungent-related components,such as 1-penten-3-one,n-pentanal dimer,2-butylfuran,and methyl thiocyanate in E.rutaecarpa-processed Coptidis Rhizoma,which correlated with the introduction of E.rutaecarpa juice.The processing of E.rutaecarpa-processed Coptidis Rhizoma significantly altered the composition of volatile components by introducing chemical constituents from E.rutaecarpa juice and promoting chemical reactions,thereby enhancing the characteristic"pungent"odor profile.The study provides a reference for the scientific processing of E.rutaecarpa-processed Coptidis Rhizoma decoction pieces.
作者
孟令邦
严林
贾哲
李颖
程莹莹
王云
金敏
张村
MENG Ling-bang;YAN Lin;JIA Zhe;LI Ying;CHENG Ying-ying;WANG Yun;JIN Min;ZHANG Cun(Institute of Chinese Materia Medica,China Academy of Chinese Medical Sciences,Beijing 100700,China;Guang'anmen Hospital,China Academy of Chinese Medical Sciences,Beijing 100053,China)
出处
《中国中药杂志》
北大核心
2025年第22期6352-6362,共11页
China Journal of Chinese Materia Medica
基金
国家中医药管理局中药炮制技术传承创新项目(GYZ-KJS-2022-055)
国家中医药管理局中药炮制技术传承基地项目(国中医药科技中药[2022]59号)
国家中医药管理局全国老药工传承工作室建设项目(国中医药人教函[2024]255号)
全国名老中医药专家传承工作室建设项目(国中医药人教函[2022]75号)。
关键词
萸黄连
炮制
顶空-气相色谱-离子迁移色谱(HS-GC-IMS)
挥发性成分
指纹图谱
化学计量学
相对气味活度值
Euodia rutaecarpa-processed Coptidis Rhizoma
processing
headspace-gas chromatography-ion mobility spectrometry(HS-GC-IMS)
volatile component
fingerprinting
chemometrics
relative odor activity value
