4个缬草醛类成分电喷雾质谱裂解规律研究

目的：对11-乙氧基缬草醛、11-甲氧基缬草醛、去酰基缬草醛和缬草醛在电喷雾质谱下的裂解途径进行探讨。方法：采用超高效液相色谱-线性离子阱/静电场轨道阱组合式高分辨质谱联用（UHPLC-LTQ Orbitrap MS）对4个缬草醛类对照品进行系统研究。色谱条件：采用UPLC BEH-C₁₈色谱柱（1.7 μm，2.1 mm×100 mm），流动相A为0.1%甲酸水溶液，B为乙腈，洗脱条件（0~20 min，85% A→50% A；20~25 min，50% A→20% A，25~30 min，20% A），流速为0.3 mL·min^-1，柱温30℃，检测波长288 nm，进样量2 μL。结果：4个缬草醛类成分在正离子模式下均会形成m/z 177、149、78等基本碎片离子，而11-乙氧基缬草醛和11-甲氧基缬草醛主要形成m/z 161、m/z 133、m/z 105特征碎片离子，而去酰基缬草醛和缬草醛则会形成m/z 131、m/z 103等特征碎片离子。结论：该类化合物有着较强的裂解规律，可用于缬草醛类化合物的快速结构鉴定。

Objective:To explore the fragmentation pathways of 11-ethoxyviburtinal,11-methoxyviburtinal,desacylbaldrinal and baldrinal by electrospray ionization mass spectrometry.Methods:Four reference standards were systematically investigated by ultra high performance liquid chromatography combined with linear ion trap electrostatic field orbit trap high resolution mass spectrometry (UHPLC-LTQ Orbitrap MS).UPLC analysis was performed on a BEH-C₁₈ column (1.7 μm,2.1 mm×100 mm),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,85%A→50%A;20-25 min,50%A→20%A;25-30 min,20%A).The detection wavelength was 288 nm and the column temperature was controlled at 30,and the injection volume was 2 μL.Results:The fragment ions of m/z 177,m/z 149 and m/z 78 were found in four baldrinals in positive ion mode,while the fragment ions m/z 161,m/z 133 and m/z 105 were found in 11-ethoxyviburtinal and 11-methoxyviburtinal and m/z 131 and m/z 103 were found in desacylbaldrinal and baldrinal.Conclusion:This kind of compound has strong fragmentation regularity,which can be used for the rapid structure identification of baldrinals.