【作者】 朱云祥；

【导师】 王书芳；

【作者基本信息】 浙江大学 ， 药学（专业学位）， 2016， 硕士

【摘要】 方剂现代化研究是中药现代化研究的重要组成部分,而方剂化学成分研究则是方剂现代化研究的基础。仲景方因其配伍严谨,疗效卓著,历来是方剂现代化的重点研究对象。枳实栀子豉汤、栀子甘草豉汤和栀子柏皮汤为三个出自《伤寒论》的栀子豉汤类方,目前对于这三个方剂的化学组成研究鲜有报道。本论文以这三个方剂为研究对象,主要研究内容如下:1.运用LC-IT-MS和LC-Q-TOF-MS技术对栀子甘草豉汤和栀子柏皮汤的化学成分进行定性研究,建立了以LC-MS为导向,采用半制备液相色谱微量制备,并采用包括1D-NMR和2D-NMR技术快速分离鉴定方剂中同分异构体的策略。两个方剂共检测到148个色谱峰,鉴定或推测出其中119个成分,其中20个成分通过与标准品对照确定其结构。21个未知成分通过本文提出的策略进行单体制备并经MS、1D-NMR和2D-NMR确证了其结构(包括3个新化合物:两个三萜皂苷和一个黄酮类化合物),其中化合物122、125和129,131、136和140,134和145,48和50,62a、62b、93和97分别为同分异构体。本文还对方剂中检测到的生物碱类化合物及京尼平龙胆双糖苷的酚酸类衍生物进行了质谱裂解规律总结。2.采用LC-IT-MS和LC-TOF-MS技术首次对枳实栀子豉汤进行了化学成分鉴定,共检测到79个色谱峰,鉴定或推测出其中39个化合物结构,包括8个环烯醚萜类化合物、5个单萜类化合物、17个黄酮类化合物、2个有机酸类化合物、2个环肽类化合物、1个生物碱类化合物和4个其他类化合物。通过与组方药材的质谱数据比对,对鉴定的各化合物来源药材进行了归属。本文同时采用第二章提出的研究策略制备得到三个多甲氧基黄酮。更多还原

【Abstract】 The modernization study of formula is an important part of TCM’s modernization.Moreover,the studies on the chemical constituents of TCM formula is the basis of formulae’s modernization research.Zhong-Jing-Fang is regarded as a main object for the modernization of formula by its rigorous compatibility and excellent therapeutic effect.Zhishi-Zhizi-Chi-Tang,Zhizi-Gancao-Chi-Tang,and Zhizi-Baipi-Tang are three TCM formulae from Shang-Han-Lun.However,the constituents in the three formulae have been rarely reported.In this work,these three formulae were selected as the research object,and the main topics of this thesis are as follow:1.The LC-IT-MS and LC-Q-TOF-MS methods were applied to the qualitative analysis of ZZGCCT and ZZBPT,a strategy based on semi-preparative LC guided by LC-MS was used to prepare the target isomers in microscale for the following off-line NMR analysis,including 1D-NMR and 2D-NMR.A total number of 148 constituents were detected,and 119 ones were identified tentatively or unambiguously.Among them,20 constituents were characterized unambiguously by comparing with the reference substances.In addition,21 constituents without reference substances were prepared and their structures were unambiguously identified by MS,1D-NMR,and 2D-NMR(including three novel compounds:two triterpenoid glycosides and one flavonoid glycoside).Among them,compounds 122,125,and 129,as well as 131,136,and 140,134 and 145,48 and 50,62a,62b,93,and 97,were several groups of isomers.The fragmentation patterns of alkaloids and phenolic acid derivatives of genipin gentiobioside detected in the two formulae were summarized.2.The qualitation of chemical constituents in ZSZZCT was first carried out by LC-IT-MS and LC-TOF-MS.A total of 79 chromatographic peaks were detected,and 39 compounds were confirmed or assumed,including 8 iridoid glycosides,5 pyronane monoterpenoid glycosides,17 flavonoid glycosides,2 organic acids,2 cyclic peptides,1 alkaloid and four other categories of compounds.The source from which crude drug of all the constituents were assigned according to the LC-IT-MS data.The strategy proposed in the second chapter was used in prepareing three polymethoxy flavonoids.更多还原