Dimension-Enhanced Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry Combined with Intelligent Peak Annotation for the Rapid Characterization of the Multiple Components from Seeds of Descurainia sophia

The complex composition of herbal metabolites necessitates the development of powerful analytical techniques aimed to identify the bioactive components.The seeds of Descurainia sophia(SDS)are utilized in China as a cough and asthma relieving agent.Herein,a dimension-enhanced integral approach,by combining ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry(UHPLC/IMQTOF-MS)and intelligent peak annotation,was developed to rapidly characterize the multicomponents from SDS.Good chromatographic separation was achieved within 38 min on a UPLC CSH C18(2.1×100 mm,1.7μm)column which was eluted by 0.1%formic acid in water(water phase)and acetonitrile(organic phase).Collision-induced dissociation-MS^(2)data were acquired by the data-independent high-definition MS^(E)(HDMS^(E))in both the negative and positive electrospray ionization modes.A major components knockout strategy was applied to improve the characterization of those minor ingredients by enhancing the injection volume.Moreover,a self-built chemistry library was established,which could be matched by the UNIFI software enabling automatic peak annotation of the obtained HDMS^(E)data.As a result of applying the intelligent peak annotation workflows and further confirmation process,a total of 53 compounds were identified or tentatively characterized from the SDS,including 29 flavonoids,one uridine derivative,four glucosides,one lignin,one phenolic compound,and 17 others.Notably,four-dimensional information related to the structure(e.g.,retention time,collision cross section,MS^(1)and MS^(2)data)was obtained for each component by the developed integral approach,and the results would greatly benefit the quality control of SDS.

Rapid Profiling and Characterization of the Multicomponents from the Root and Rhizome of Salvia miltiorrhiza by Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry in Combination with Computational Peak Annotation Workflows

Herbal components characterization represents a challenging task because of the co-existing of multiple classes of naturally occurring compounds with wide spans of polarity,molecular mass,and the ubiquitous isomerism.The root and rhizome of Salvia miltiorrhiza have been utilized as a reputable traditional Chinese medicine Salviae Miltiorrhizae Radix et Rhizoma(Dan-Shen)in the treatment of cardiovascular disease.Herein,a dimensionenhanced ultra-high performance liquid chromatography/ion mobility/quadrupole time-of-flight mass spectrometry approach in combination with intelligent peak annotation workflows was established aimed to rapidly characterize the multicomponents from S.miltiorrhiza.Due to the sufficient optimization,satisfactory chromatography separation was enabled on an HSS T3 column within 33 min using 0.1%formic acid in water(A)and acetonitrile(B)as the mobile phase,while the data-independent HDMS^(E) in both the negative and positive electrospray ionization modes was utilized for the high-coverage MS^(2) data acquisition.Streamlined automatic peak annotation by searching an in-house library(recording 198 known compounds)followed by the subsequent confirming steps(e.g.,comparison with the reference compounds,fragmentation pathways analysis,and retention behavior comparison,etc.),allowed us to identify or tentatively characterize a total of 86 components(including 50 terpenoids,21 phenolic acids,and 15 others)from S.miltiorrhiza.Importantly,three-dimensional structure information,such as the retention time,MS^(1) and MS^(2) data,and collision cross section(CCS),was provided,which can facilitate the more reliable characterization of herbal components.

基于顶空进样气相色谱-质谱联用和非靶标代谢组学分析人参、西洋参和三七经蒸制后挥发性成分的转化

人参是全世界范围内广受欢迎的滋补品,经蒸制后补益效果更佳。先前对人参蒸制的研究主要集中在所含的皂苷,但对其挥发性成分研究较少。本研究建立了顶空进样气相色谱-质谱联用结合非靶标代谢组学方法,对人参、西洋参和三七在蒸制过程中挥发性成分的变化进行整体性表征。通过优化GC-MS色谱分离条件,采用HP-5MS弹性石英毛细管柱在38分钟内实现对人参、西洋参和三七生品及蒸制品(1-10 h)中挥发性成分的表征。从人参、西洋参和三七中分别鉴定出了106、106和105种挥发性成分。多元统计分析可以描述不同蒸制时间介导的人参、西洋参和三七的转化轨迹。最终,通过基于GC-MS的非靶标代谢组学分析,发现人参、西洋参和三七蒸制过程中分别有13、16和14种差异成分。值得注意的是,其中异戊醇、2-正戊基呋喃、正己醛、丁香烯和(-)-马兜铃烯可以区分人参的生品和炮制品;α-蒎烯、2-正戊基呋喃、己酸、2,3-丁二醇和丙酮酸可以区分西洋参生品和炮制品;莎草烯、糠醛、Δ-杜松烯、羟基丙酮和1-戊醇可以区分三七生品和炮制品。本研究所建立的气相色谱-质谱联用方法可以揭示中药中挥发性成分的变化,为进一步探讨中药炮制机理提供一种实用的分析工具。