天然染料质谱数据库的建立与应用  

Establishment and application of mass spectral database for natural dyes

作　　者：寿晨超 娜仁高娃 高素芸 刘剑[1,3] 赵丰 SHOU Chenchao;NARENGGAOWA;GAO Suyun;LIU Jian;ZHAO Feng(College of Textile Science and Engineering(International Institute of Silk),Zhejiang Sci-Tech University,Hangzhou,Zhejiang 310018,China;Museum of Bayinguoleng Mongol Autonomous Prefecture,Korla,Xinjiang 841001,China;Key Research Base for Textile Conservation,State Administration for Culture Heritage,China National Silk Museum,Hangzhou,Zhejiang 310012,China)

机构地区：[1]浙江理工大学纺织科学与工程学院(国际丝绸学院),浙江杭州310018 [2]巴音郭楞蒙古自治州博物馆,新疆库尔勒市841001 [3]中国丝绸博物馆纺织品文物保护国家文物局重点科研基地,浙江杭州310012

出　　处：《纺织学报》2023年第11期120-131,共12页Journal of Textile Research

基　　金：国家重点研发计划项目(2019YFC1520302)。

摘　　要：为提高纺织品文物中天然染料鉴定的准确性和便捷性,利用高效液相色谱-质谱联用(HPLC-MS)技术对68种天然染料化合物标准品进行分析,收集化合物分子质量、碎片离子及丰度、检测离子模式、保留时间等信息,建立了基于美国国家标准技术研究院质谱数据库的天然染料质谱数据库。通过设置合理的检索条件,确定质谱库检索最佳参数,对代表性蒽醌类(茜素)、黄酮类(槲皮素、木犀草素)、生物碱类(小檗碱)化合物进行了分子碎裂机制解析。应用自建的质谱数据库成功实现了2件古代纺织品文物中天然染料的快速鉴定,质谱数据库检索结果显示其含有茜素、茜紫素、木犀草素、小檗碱、巴马汀等染料化合物,且在文物样品的检索过程中,质谱数据库正向检索匹配度与反向检索匹配度均大于800,匹配率均在95%以上。利用质谱数据库检索技术鉴定天然染料具有可行性,为纺织品文物中天然染料的研究工作提供了新思路。Objective There are different types of natural dyes,including indoles,anthraquinones,naphthoquinones,flavonoids,alkaloids,curcumins,and so on.Facing a large number of textile culture relics,it is impossible to identify quickly the dye compounds only by manual identification using spectral or chromatographic analysis techniques.This research aims to establish a mass spectral database of natural dyes.Using the retrieval technology of the mass spectrum database,the components of natural dyes in textile cultural relics would be identified quickly,bringing efficiency and convenience for the identification of natural dyes in the future.Method In this study,standard natural dye compounds were analyzed by high performance liquid chromatography-mass spectrometry(HPLC-MS),and mass spectrum data were collected.The natural dye mass spectral database was established using National Institute of Standards and Technology(NIST)spectral database software.The search parameters of the software were optimized to achieve the best search results.By comparing the relative peak strength and mass of the unknown mass spectrum with the standard mass spectrum in the database,the similarity between them was identified,and the search result was finally determined.Results Samples of the natural dyes were analyzed by HPLC-MS to obtain their total ion chromatogram data(Tab.1).The appropriate chromatographic peak was selected using Thermo Xcalibur Qual Browser software(Fig.1),the MS/MS spectra of natural dye compounds were exported to NIST MS Search 2.3 software before entering the information of the compounds such as name,formula,molecular weight,synonyms,detection ion mode,retention time,and chemical structure into the self-built mass spectral database.The above operations were repeated until the mass spectral database was established.In order to identify the molecular structure of dye compounds,it is necessary to analyze the mechanism of MS/MS fragmentation.Fragmentation pathways of alizarin,quercetin and luteolin were analyzed,and the derivati

关 键 词：质谱检索 天然染料 高效液相色谱-质谱联用技术 美国国家标准技术研究院质谱数据库 多级质谱 

分 类 号：TS193.1[轻工技术与工程—纺织化学与染整工程]