甘松新酮、去氢木香内酯和甘松香酮H—3个倍半萜类成分的电喷雾质谱裂解规律研究

Nardosinone,Dehydrocostus Lactone and Kanshone H-Fragmentation Rules of Three Sesquiterpenoids Based on Electrospray Ionization Mass Spectrometry

目的对甘松新酮、去氢木香内酯和甘松香酮H在高分辨电喷雾质谱下的裂解途径进行分析,并探讨其母核结构及可能的裂解行为。方法采用UHPLC-Q-Exactive Orbitrap MS高分辨质谱对3个倍半萜类化学成分对照品裂解规律进行系统研究。色谱条件:采用UHPLC BEH C18色谱柱(2.1 mm×50 mm,1.7μm),流动相0.1%甲酸水(A)-乙腈(B),洗脱条件(0-20 min,95%A→15%A;20 min-25 min,15%A→95%A;25 min→35 min,95%A),流速为0.3 mL·min-1,柱温25℃,进样量5μL。结果甘松新酮在MS正离子模式下主要形成m/z233、179、135、107等特征碎片离子;去氢木香内酯在MS正离子模式下主要形成m/z195、185、175、143等特征碎片离子;甘松香酮H在MS正离子模式下主要形成m/z175、161、107等特征碎片离子。结论甘松中主要3种类型的倍半萜类对照品有可循的裂解规律,可用于甘松中纳多西烷型、愈创木烷型和马兜铃烷型及其他类似结构倍半萜成分的快速结构鉴定与分析。

Objective To explore the fragmentation pathways of kanshone H,dehydrocostus lactone and nardosinone by UHPLC-Q-Exactive Orbitrap MS.Methods Three reference standards were systematically investigated by ultra-high performance liquid chromatography combined with ultra-high performance liquid chromatography coupled with quadrupole/electrostatic field Obitrap high-resolution mass spectrometry(UHPLC-Q-Exactive Orbitrap MS).UPLC analysis was performed on a BEH C18 column(2.1 mm×50 mm,1.7μm),with a mobile phase consisting of 0.1%formic acid(A)–acetonitrile(B)at the flow rate of 0.3 mL·min-1(0-20 min,95%A→45%A;20-30 min,45%→5%;30-35 min,5%).The detection column temperature was controlled at 25℃,and the injection volume was 5μL.Results The fragment positive ions of m/z 233,179,135,107 were found in nardosinone;the fragment positive ions of m/z 195,185,175 and 143 were found in dehydrocostus lactone;the fragment positive ions of m/z 175,161 and 107 were found in kanshone H.Conclusion Three types of sesquiterpenes standards in Nardostachys Radix et Rhizoma which can be cracked regularly.It can be used for rapid structural identification of aristolochane type,guaiacane type,nadoxane type and other similar structures of sesquiterpene in Nardostachys Radix et Rhizoma.