Determination of flavone, flavonol, and flavanone aglycones by negative ion liquid chromatography electrospray ion trap mass spectrometry
Determination of flavone, flavonol, and flavanone aglycones by negative ion liquid chromatography electrospray ion trap mass spectrometry
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DOI：
10.1016/s1044-0305(01)00226-4
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发表时间：
2001-06-01
影响因子：
3.2
通讯作者：
Quetin-Leclercq, J
中科院分区：
文献类型：
--
作者：
Fabre, N;Rustan, I;Quetin-Leclercq, J
采用高效液相色谱法分离了11种天然黄酮苷元，分别属于黄酮类、黄酮醇类和黄烷酮类化合物，并采用电喷雾串联质谱（ESI-MS/MS）进行了分析。为了解析获得的MS/MS光谱，使用离子阱质谱仪通过直接环进样重新研究每种化合物。通过对五种互补的合成黄酮苷元的分析，我们可以根据MS谱提出合理的裂解方案。本研究中研究的不同苷元的负离子ESI-MS/MS行为显示有趣的差异时，与先前描述的模式相比，使用各种电离技术在正离子。因此，关于逆狄尔斯-阿尔德（RDA）裂解途径，几个结构信息阴离子出现高度特异性的负离子模式。此外，一个新的内酯型结构，而不是乙烯酮，提出了一个经典的RDA诊断离子。我们还观察到不寻常的CO，CO2和C3 O2的损失，这似乎是负离子模式的特点。所有这些结果和这些不寻常的中性损失表明，负离子模式是一个强有力的补充工具的正离子模式的结构表征黄酮苷元的ESI-MS/MS。（C）2001年美国质谱学会。
Eleven naturally occurring flavonoid aglycones, belonging to the representative flavone, flavonol, and flavanone types were separated by high performance liquid chromatography and analyzed on-line with negative ion electrospray ionization tandem mass spectrometry (ESI-MS/MS). In order to resolve the MS/MS spectra obtained, each compound was reinvestigated by direct loop injections using an ion trap mass spectrometer. The MS " spectra obtained allowed us to propose plausible schemes for their fragmentation supported by the analysis of five complementary synthetic flavonoid aglycones. The negative ion ESI-MS/MS behavior of the different aglycones investigated in this study revealed interesting differences when compared with the previously described patterns obtained using various ionization techniques in positive ion. Thus, concerning the retro Diels-Alder (RDA) fragmentation pathways, several structurally informative anions appeared highly specific of the negative ion mode. In addition, a new lactone-type structure, instead of a ketene, was proposed for a classic RDA diagnostic ion. We also observed unusual CO, CO2, and C3O2 losses which appear to be characteristic of the negative ion mode. All these results and these unusual neutral losses show that the negative ion mode was a powerful complementary tool of the positive ion mode for the structural characterization of flavonoid aglycones by ESI-MS/MS. (C) 2001 American Society for Mass Spectrometry.