摘要
本论文采用正负离子检测模式的(±)ESI-MS~n方法分别对含有单糖或双糖的黄酮糖苷类化合物(包括黄酮醇O-单糖苷类、黄酮O-单糖苷类、黄酮醇O-双糖苷类、黄酮O-双糖苷类、黄酮醇O-乙酰基糖苷类和黄酮醇3,7-二-O-糖苷类化合物等)的质谱行为进行了详细的分析研究,掌握了该类化合物结构特征与质谱裂解行为之间的相关性,重点归纳及总结了这类化合物在负离子模式的电喷雾电离条件下的质谱裂解特征,尤其在确定黄酮糖苷类化合物的糖基化位置及糖链连接顺序方面取得了新的突破。在此基础上,采用直接进样的ESI-MS~n、LC-UV-MS及LC-UV-MS~n等方法,对药用植物活性提取物中相同结构类型的成分进行了分子鉴别及结构解析。通过本项研究建立了简便、快速分析与鉴定黄酮苷类化合物的质谱分析方法,并以此作为分析药用植物混合物中相关成分的主要依据,共分析推断了黄花柳植物中三个活性提取物的31个成分的可能结构,同时与对照品进行比较,确认了19个组分的结构。
本论文研究的具体内容主要包括以下四个部分:
1.黄花柳植物中黄酮类成分的分离与鉴定
本论文对维吾尔民间药材黄花柳植物中的黄酮类成分进行了提取分离与鉴定研究,通过不同的色谱分离纯化手段,获得了含量较多的11个黄酮类成分,其结构经1D、2D NMR和MS方法得以确定为异鼠李素3-O-β-D-(6″-O-乙酰基)-葡萄糖苷(1)、山柰素3-D-β-D-(6″-O-乙酰基)-葡萄糖苷(2)、槲皮素3-O-β-D-(6″-O-乙酰基)-葡萄糖苷(3)、异鼠李素3-O-β-D-葡萄糖苷(4)、槲皮素3-O-β-D-葡萄糖苷(5)、杨梅黄素3-O-β-D-葡萄糖苷(6)、山柰素3-O-云香糖苷(7)、槲皮素3-O-芸香糖苷(8)、槲皮素3,7-二-O-β-D-葡萄糖苷(9)、异鼠李素3,7-二-O-β-D-葡萄糖苷(10)、杨梅黄素3,7-二-O-β-D-葡萄糖苷(11)。其中除化合物10外,其余化合物均为首次从该植物中分离得到。另外,经药理活性筛选,其提取物Sc-T、Sc-O和Sc-N、具有一定的药理作用。本研究为阐明黄花柳的化学成分组成和结构特点及其药理作用研究提供了一定的科学依据。
A series of flavonoid glycosides including flavonoid O-glycosides, flavonoid O-diglycosides, flavonol O-acetylglycosides and flavonol 3,7-di-Oglycosides were systematically investigated by positive and negative ion electrospray ionization tandem mass spectrometry (ESI-MS~n ). The relationship between their structural features and the corresponding characteristic fragmentation behavior was investigated and the formation of characteristic ions and the factors influencing theirs intensities were also discussed. Particularly, a novel analytical idea was put forwarded to determine the glycosylation position and saccharidic sequence. At last, rapid and effective analytical method were established through investigating and summarizing the fragmentation behavior of these compounds which can be benefit to analyze the related constituents in medicinal plant crude extracts. Based on the fragmentation rules and analytical methods established previously, three crude extracts were analyzed by ESI-MS~n, LC-UV-MS and LC-UV-MS~n techniques, and the possible structures of thirty-one components including known and unknown compounds were inferred, some of them were confirmed by comparing with the standards.
1. Isolation and identification of flavonoid compounds from Salix caprea L.
Flavonoid constituents in the pollen of Salix caprea Z.(Uyghur Medicinal Plant) were isolated by chromatographic techniques, and eleven main constituents were obtained. Their structures were identified by NMR and MS techniques. The structure of these compounds are as follows: isorhamnetin 3-O-β-D-(6"-O-acetyl)- glucoside(l), kaemferol 3-O-β-D-(6"-O-acetyl)-glucoside(2), quercetin 3-O-β-D-(6"-O-acety)-glucoside(3), quercetin 3-O-β-D-glucoside(4), isorhamnetin 3-O-β-D-glucoside glucoside(5), myricetin 3-O-β-D-glucoside(6), kaempferol 3-O-rutinoside(7), quercetin 3-O-rutinoside(8), quercetin 3,7-di-O-glucoside(9), isorhamnetin 3,7-di-Oglucoside(10), myricetin 3,7-di-Oglucoside(11). Except compound 10, all compounds were isolated from pollen of Salix caprea L for the first time. This study
引文
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