南京椴花化学成分鉴定及不同发育时期黄酮类化合物差异分析

Identification of chemical composition and metabolic analysis of flavonoids in flowers of Tilia miqueliana Maxim.

【目的】研究南京椴花化学成分及其主要成分黄酮类化合物在不同发育时期的变化规律,为后续采用多组学手段探究椴树花中重要药用化合物的代谢通路及调控机制解析奠定基础,同时为椴树花的采收提供理论依据。【方法】以10年生南京椴为试验材料,用超高效液相色谱串联质谱(UPLC-MS/MS)技术分析南京椴花中代谢物组分及类黄酮含量差异。【结果】(1)南京椴花中共鉴定得到46种化合物,其中有机酸及其衍生物13种、香豆素及其衍生物4种、酯1种、类黄酮28种。(2)盛花期是南京椴花中代谢物发生显著变化的分界点,与蕾期相比,开花期间代谢物变化更明显。(3)多重比较分析显示:26种黄酮类化合物在不同时期花中含量差异显著(P<0.05),阿福豆苷、山奈苷、槲皮苷、橙皮苷、花旗松素和芹菜素-7-O-葡萄糖醛酸在盛花期相对含量较高,原花青素A2和3种原花青素三聚体在末蕾期含量较高。【结论】发育状态可作为判断南京椴花中次级代谢物含量的重要因素,末蕾期的标志性化合物是原花青素A2,盛花期的标志性化合物是芹菜素-7-O-葡萄糖醛酸,末蕾期和盛花期均具有采收价值。

[Objective]To lay a foundation for the use of multi-omics methods to explore the metabolic pathways and regulatory mechanisms of important medicinal compounds of Tilia miqueliana Maxim.and to provide a basis for the harvesting of flowers,the chemical composition of T.miqueliana flowers,the content changes of its signature components(flavonoids)at different growing stages were investigated.[Methods]The 10-year-old T.miqueliana was used as the test material.The experiments were conducted to analyze chemical components of flowers and differences in flavonoid contents using ultra performance liquid chromatography tandem mass spectrometry(UPLC-MS/MS).[Results](1)A total of 46 compounds were identified,including 13 organic acids and their derivatives,4 coumarins and their derivatives,1 ester,and 28 flavonoids.(2)Flower opening stage was the cut-off point for significant changes in metabolites.Compared with the bud stage,the metabolites changed more significantly during flowering.(3)Multiple comparison analysis showed that the content of 26 flavonoids differed significantly(P<0.05)in flowers at different phenological stages.Afzelin,kaempferitrin,quercitrin,hesperidin,taxifolin,and apigenin 7-O-glucuronide were higher at flower opening stage.Final bud stage had higher concentration of proanthocyanidin A2 and three proanthocyanidin trimers.[Conclusion]The development status may be an important factor in determining the content of secondary metabolites in the flowers of T.miqueliana.The signature compound at the final bud stage was proanthocyanidin A2 and at full bloom stage was apigenin-7-O-glucuronide,both of them were valuable for harvesting.