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题名: 龙血竭研究
作者: 郑庆安
学位类别: 博士
答辩日期: 2003
授予单位: 中国科学院昆明植物研究所
授予地点: 中国科学院昆明植物研究所
导师: 杨崇仁
关键词: 血竭 ; 龙血竭 ; 剑叶龙血树 ; 龙血树 ; 资源考证 ; 化学成分 ; 指纹图谱 ; 质量标准 ; 形成机制 ; 植物防卫系统
学位专业: 植物学
中文摘要: 本论文共由六章组成。第一章对血竭的基原进行了考证,对国产龙血竭的发现及其意义进行了评价,并对国内外血竭(dragon'sblood州化学研究进展进行了系统的介绍。第二章详细论述了国产龙血竭基原植物剑叶龙血树(Dracaenacochinchi。ensisS.C.Chen)新鲜树千化学成分的研究。第三章在已有的基础上对我国生产龙血竭的化学成分作了进一步的深入研究。第四章建立了龙血竭高压液相色谱分析技术,对我国不同产地生产的龙血竭进行了分析,对其中部分成分进行了定量分析,同时应用指纹图谱分析方法对龙血竭原料进行了相似度分析。第五章利用化学和生物学手段对血竭形成机制进行了初步探讨。第六章以植物防卫系统为主题,简要综述了有关植物抗逆反应分子基础的一些研究进展。一、世界各地产血竭(Dragon'sblood)的基源分属于4科5属约20余种植物。其中,龙舌兰科龙血树属植物约45种,如产于北非、西亚和阿拉伯地区的索科特拉龙血树(D。caenacinnabariBalff),龙血树(D.dracoL.),以及阿拉伯龙血树(D.schizantha)均为血竭最早的基源植物。东南亚地区如泰国、越南、柬埔寨产的龙血树属植物D.loureiri也可形成血98。随着新大陆的开发;欧洲人在南亚、非洲和美洲也不断发现Dragon'sblood的代用品,主要为来源于大我科巴豆属和豆科紫檀属植物的树脂。印度部分地区使用的血竭除龙血树(D.dracoL.)外,还有豆科植物Pie。carp。办aco,棕搁科植物出bm。sdaco等分泌的红色树脂。印度尼西亚、马来西亚等地产的棕桐科麒麟竭(DaemonompdracoBl.)作为血竭资源在我国使用,应追溯于宋朝,发展于明清。以上各种血竭由于基原来自不同科属的植物,化学成分有显著的差异,显然不宜互相代用。七十年代蔡希陶教授在云南南部发现剑叶龙血树[D.cochinchinensts(Lou.)S.C.Chen]树干可形成红色树脂,与血竭最早的基原植物龙血树为同科同属植物,二者产生的树脂亦相近,从而开发成功国产血竭(龙血竭),并澄清了长期以来我国血竭基原的混乱现象。目前,龙血竭已成为我国中药产业的重要原料。H、对云南西双版纳采集的剑叶龙血树[D.cochincbinensi3(Lour)S.C,Chen]新鲜树干进行了系统的化学研究,共分离鉴定了38个化合物。其中包括22个笛体两己糖体(18个新化合物),6个酚甙,7个黄酮类(1个新化合物)以及三个省醇类成分。笛体配糖体包括有吹笛、螺笛、呋环螺笛、C-22孕笛、C-21孕笛等多种类的笛体骨架.应用光谱和波谱技术,特别是应用二维核磁共振技术解析了19个新化合物的结构。配糖体中糖基的构型通过GC-MS与标准糖比较推定。研究发现剑叶龙血树中奋体配糖体的甙元以在奋体骨架的C.14位具有羟基取代为特征。三、在前NBI一究的基础上,对龙血竭进行了深入的化学成分研究,共分离到40个化合物。其中30个黄酮类化合物(11个新化合物);四个笛醇美成分(2个新化合物),两个木脂素;两个二苯乙烯类成分,一个笛体皂旮。应用光谱和波谱技术,特别是应用二维核磁共振技术和X.单晶衍射技术解析了14个新化合物的结构。首次从龙血树属植物产的血竭中分离鉴定两个红色成分。首次从自然界得到一个C环裂环重排的笛醇。首次从国产血竭中分离鉴定查耳酮的三聚体。四,建立了龙血竭的高压液相色谱分析技术,指认了龙血竭液相色谱图中的28个峰,并对其中主要成分进行了定量分析。建立了指纹图谱分析模式。主要成分分析表明;云南和广东产龙血竭基本一致,而与广西产龙血竭差别较大。以龙血素A和龙血素B的高压液相色谱含量分析手段为基础,提出云南龙血竭和广西龙血竭应于以区别的建议,并拟订了云南龙血竭新的质量标准。五,利用高压液相色谱技术进一步比较了广西产龙血竭和云南产龙血竭的差异,结果表明,广西产龙血竭以二苯乙烯类化合物为主。云南产龙血竭则以二氢查耳酮类成分为主,研究认为,在确认二者为同一物种的前提下。剑叶龙血树可能存在两个化学型。六、依据植物次生代谢产物分子进化的原理,对龙血竭中酚类化合物形成的生源途径提出了假设。在此基础上,利用高压液相色谱技术对剑叶龙血树树干栓皮部、正常生长的叶、受感染的叶、以及树千上寄生的拟红革盖菌子实体、菌丝体、以及地衣等的化学成分进行了初步的比较分析。结果提示龙血竭的形成与剑叶龙血树树干的损伤和微生物的侵染均有一定的关系,其形成的机理尚有待进一步的深入研究。同时,比较了龙血竭和引种的非洲龙血树树脂的谱图特征,后者以含高异黄酮类成分为主,与云南龙血竭和广西龙血竭均有显著差异。七,简要综述了植物防卫系统的部分研究进展。包括植物R基因介导的防卫反应,R蛋白的研究进展,水杨酸、茉莉酸以及乙烯在植物防卫反应中的作用,以及植物抗毒素的研究进展等。
英文摘要: This dissertation is composed of six chapters. In the first chapter, the author made a textual research of the origin plants of dragon's blood and summarized the chemical study of dragon's blood. In chapter 2, the chemical constitutes of the fresh stems of Dracaena cochinchinensis was carefully investigated. In chapter 3, a continuation study on the chemical constituents of dragon's blood of D. cochinchinensis was carried out. In chapter 4, a fingerprint analysis method was established and a quantitative analysis was conducted on dragon's blood of D. cochinchinensis. Based on this study, a new analytical standard was proposed. Chapter 5 introduces some experiments for revealing the ecological mechanism of dragon's blood was performed. In chapter 6, the author simply summarizes the recent research on the study of plant defense system in which included the significance of the R protein, methyl salicylate, methyl jasmonate, ethylene and phytoalexins. Dragon's blood was used by local people to treat many kinds of diseases for more than 3000 years. The origin plants of dragon's blood came from 4 families 5 genus. Those used in south American Amazon valley region were from some species of Croton (Euphorbiaceae); while in China, middle-eastern Asia and West Africa, they came from some species of Dracaena (Agavaceae); In India, they were from 2-3 species of Pterocarpus (Leguminosae); In southeast Asian Malaysia and Indonesia, they came from some species of Daemonorops (Palmae); Calamus draco was also used as an original plant of dragon's blood in some place of India. From the methanolic extract of the fresh stems of D. cochinchinensis, 38 compounds were isolated and their structures were identified by means of spectral and chemical methods. Twenty-two are steroidal glycosides of which 18 are new compounds. Most of the steroidal saponins are epimers of 25R and 25S. Six are phenolic glycosides. Seven are flavanoids including a new meta-homoisoflavane. Three are simple sterols. 3, In a continuation study on the chemical constituents of dragon's blood of D. cochinchinensis, forty compounds were isolated. They were 30 flavonoids of which 12 are new ones, six are steroid compounds (2 new sterols), 2 stilbenes, and 2 lignans. This is the first report that two red color compounds identified from dragon's blood of Dracaena. A seco-C-ring rearrangement sterol was the first example of such skeleton from nature, and its structure was established by means of 2D-NMR technique and X-ray crystallographic analysis. The triflavonoids were first examples from dragon's blood of D. cochinchinensis. A HPLC fingerprint analysis method was established and used in the analysis of the relationship of dragon's blood of D. cochinchinensis from different regions. A quantitative study of dragon's blood was conducted. Based on this study, a new standard of dragon's blood of D. cochinchinensis was proposed. The ecological mechanism of dragon's blood were tentatively investigated. It was found that the major compounds in dragon's blood of Dracaena were quite different. Those produced in Guangxi province, stilbenes are major compounds. Those produced in Yunnan and Guangdong province, dihydrochalcones are major compounds. The resin came from D. draco was mainly composed of homoisoflavonoids. A HPLC analysis of the extracts of the mycelium and fruiting body of Coriolopsis sanguinaria, a species of lichen Parmotrema tinctorum (Delise ex Nyl.) Hale, the leaves of D. cochinchinensis were conducted. The ether extract of dragon's blood were analyzed by means of GC-MS, it is interesting that the volatile constituents didn't contain methyl jasmonate and methyl salicylate. The recent advance on the study of some aspects of plant defense system were simply summarized.
语种: 中文
内容类型: 学位论文
URI标识: http://ir.kib.ac.cn/handle/151853/690
Appears in Collections:昆明植物所硕博研究生毕业学位论文_学位论文

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龙血竭研究.郑庆安[d].中国科学院昆明植物研究所,2003.20-25
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