Identification of regioisomers of methylated kaempferol and quercetin by ultra high performance liquid chromatography quadrupole time-of-flight (UHPLC–QTOF) tandem mass spectrometry combined with diagnostic fragmentation pattern analysis

化学 结构异构体 串联质谱法 山奈酚 质谱法 黄酮醇 碎片(计算) 色谱法 电喷雾电离 槲皮素 立体化学 有机化学 计算机科学 操作系统 抗氧化剂
作者
Chengying Ma,Haipeng Lv,Xinzhong Zhang,Zongmao Chen,Jiang Shi,Meiling Lu,Zhi Lin
出处
期刊:Analytica Chimica Acta [Elsevier]
卷期号:795: 15-24 被引量:24
标识
DOI:10.1016/j.aca.2013.07.038
摘要

The O-methylation of active flavonoids can enhance their antiallergic, anticancerous, and cardioprotective effects depending on the methylation position. Thus, it is biologically and pharmacologically important to differentiate methylated flavonoid regioisomers. In this study, we examined the regioisomers of methylated kaempferol and quercetin using ultra high performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry. The methyl groups on the flavonoids can generally be cleaved as methyl radicals in a position-independent manner. We found that methyl groups can be cleaved as methane. If there are protons adjacent the methoxy on the flavonol rings, intra-molecule proton transfer can occur via collision-induced dissociation, and one molecule of methane can then be eliminated. The remaining charged fragment ([M+H-CH4](+)) reflects the adjacent structure and is specific to the methoxy position. Furthermore, the retro Diels-Alder (RDA) fragmentation of methylated flavonols can generate fragments with the methoxy at the original methylated ring. Combining the position-specific [M+H-CH4](+) fragment with the RDA fragments provides a diagnostic pattern for rapidly identifying methylated regioisomeric flavonols. Along with their retention behaviour, we have successfully identified ten regioisomers of methylated kaempferol and quercetin, which include six compounds previously reported in plants and shown to be biologically active. The developed approach is sensitive, rapid, reliable, and requires few standard compounds. It is highly efficient for characterising the specificity of novel flavonoid O-methyltransferases and can help direct enzymatic or chemical syntheses during the early stages of drug discovery. This method also has potential for use in identifying other methylated isomeric flavonoids.
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