【作者】 王俊龙；

【导师】 王一峰； 张继；

【作者基本信息】 西北师范大学 ， 植物学， 2007， 硕士

【摘要】 甘肃风毛菊（Saussurea kansuensis Hand.-Mazz.）,隶属于菊科风毛菊属植物,多年生无茎莲座状草本,分布于西固、岷山3600-3700m间,为甘肃特有种,是我国传统的药用植物,具有清热解毒,祛风透疹,活血调经等功效。本文首次系统的研究了生长于甘肃省甘南卓尼县甘肃风毛菊全草的化学成分。用常规的溶剂分配、硅胶柱层析、制备薄层层析、重结晶等手段从甘肃风毛菊全草甲醇提取物的石油醚部分和乙酸乙酯部分中分离得到14个化合物,并用1D NMR:¹H NMR,¹³C NMR,DEPT;IP;MS等波谱技术,结合标样对照,鉴定了其结构。其中一个初步确定为新化合物,命名为:1β,3β-二羟乌苏-9（11）,12-二烯-十六烷酸酯（1）;另外13个为已知化合物8α-11β-dihydroxy-1（10）,8α-11β-二氢-1（10）,-愈创二烯-12,6-内酯-2-酮-O-β-D-glucopyranoside（2）、11,12,13-三羟基-4,（15）,8-桉烷-8-酮（3）、3-羟基-1（10）,3-愈创木二烯-12,6-内酯-2-酮（4）、10β-二氢-11αH-愈创木烷-4（15）-ene-12,6α-内酯（5）、3-羟基-1（10）,4-吉马二烯-12,6-内酯（6）、2α,3β,19α,30-四羟基乌索-12-烯-23,28-二酸-28-O-（6’-O-甲基-β-吡喃葡萄糖）（7）、2α,3β,19α,24-四羟基乌索-12-烯-28-甲酯（8）、20α,21α-环氧-3β,22α-双羟基蒲公英烷（9）、7α-羟基-β-谷甾醇（10）、β-胡萝卜甙（11）、麦角甾-6,22-二烯-3β,5α-三醇（12）、木犀草素（13）和β-谷甾醇（14）。利用气相色谱-质谱联用（GC-MS）技术对甘肃风毛菊9个居群全草精油的化学成分进行了分析,鉴定了69种化合物。其化学成分以倍半萜类和含氧倍半萜类化合物为主,氧化石竹烯和石竹烯为甘肃风毛菊精油的主要化学成分。聚类分析和主成分分析均可将9个居群分成3类,得到3种具有过渡特点的化学型:氧化石竹烯/顺,顺,顺-7,10,13-十六碳三烯醛、氧化石竹烯/石竹烯/δ-三环烯和氧化石竹烯/六氢甲烷薁,不同生境对不同居群精油化学成分的影响并不很显著,甘肃风毛菊种间精油化学成分的多样性与一致性并存。对甘肃风毛菊精油的抗菌活性进行了初步研究,其对枯草杆菌的抑制作用明显,在20 mg╱ml浓度下属于高度敏感,抑菌效果优于青霉素;对大肠杆菌也有一定的抑制作用,10mg/ml浓度下抑菌效果最好,而对于金黄葡萄球菌无任何抑制作用。本文对风毛菊属植物的分布进行了研究并对其化学成分及药理学研究概况做了综述。在目前对风毛菊属化学成分研究的基础上,结合植物区系地理学分析,首次对风毛菊属植物进行了化学系统学探讨。结果表明,对已报道的风毛菊属植物化学成分的不同结构类型为分类依据,与目前对多数亚属及属下组的划分较为吻合,而在风毛菊亚属中,羽裂组和纤维组都是以愈创木烷型内酯、桉烷型倍半萜和五环三萜类为主,风毛菊组中显示了较大的差异,需要进一步的化学证据来阐明其主要的化学类型。雪莲亚属和雪兔子亚属中多为黄酮类化合物,尤其以雪兔子亚属几乎以芹菜素黄酮和木犀草素类黄酮这一较雪莲亚属中的山柰酚黄酮醇和槲皮素黄酮醇等更为进化的黄酮类化合物为主,而这两个类群是受第三纪末期至第四纪初期的喜马拉雅和青藏高原的隆起、海浸海退以及第三纪和第四纪北半球冰川作用强烈影响而适应高寒严酷环境的高海拔类群,结合对其他亚属和组的分析,我们初步认为5个亚属之间的进化顺序应该是:雪兔子亚属—雪莲亚属—附片亚属—齿冠亚属—风毛菊亚属,雪兔子亚属最为进化,而风毛菊亚属最为原始。更多还原

【Abstract】 Saussurea kansuensis Hand.-Mazz,perennial stemless herbs belongs to the genus Saussurea DC in the Compositae.It is an endemic species known only from Gannan（eastern edge of Qinhai-Tibet Plateau,Gansu province）where it distributed at the altitudes from 3600m to 3700m in Xigu and Mingshan.S.kansuensis Hand.-Mazz, has long been used for traditional Chinese medicine in China with the effects of relieving internal heat and pain,harmonizing the circulation of menstrual,curing gynecology diseases.We studied the chemical constituents of S.kansuensis Hand.-Mazz. systematically in Gansu province for the first time.Fourteen chemical compounds were isolated from Pet.Et.and EtOAc.sections separately by means of solvent partition,silica gel column chromatography（CC）,preparative thin layer chromatography（TLC）and recrystallization etc.The structures of these compounds were elucidated by spectroscopic methods:IR,MS and 1D NMR(¹H NMR,¹³C NMR,DEPT).One of them was preliminary determined as new compound named 1β,3β-dihydroxyurs- 9（11）,12-diene-hexadecanoate（1）and need further study. 8α-11β-dihydroxy-1（10）,-guaiadiene-12,6-olide-2-one-O-β-D-glucopyranoside（2）、11,12,13-trihydroxy-4,（15）,8-eudesmdiene-8-one（3）、3-hydroxy-1（10）,3-guaiadiene - 12,6-olide-2-one（4）、10β-dihydroxy-11αH-guaia-4（15）-ene-12,6α-olide （5）、3-hydroxy-1（10）,4-germadiene- 12,6-olide（6）urs-2α,3β,19α,30-tetrahydroxy-12-ene-23,28-dioicacid- 28-0-（6’-O-methyl-β-D-glucopyranosyl）（7）、urs-2α,3β,19α,24-tetrahydroxy-12-ene- 28-oic ester（8）、3β,22α-dihydroxyl-20α, 21α-epoxy-taraxasta（9）、stigmast-5-ene-3β,7α-diol（10）、β-daucosterol（11）、ergosterol peroxide（12）、luteolin（13）andβ-sitosterol（14）。The essential oils of S.kansuensis Hand.-Mazz.were obtained by hydrodistillation and subjected to detailed GC/MS analysis in order to determine possible similarities among 9 populations and also the differences in their chemical compositions from a chemotaxonomic point of view.A total of 69 compositions were identified and indicated that sesquiterpene hydrocarbons and oxygenated sesquiterpenes were the main components.Cluster analysis and principal component analysis（PCA）of identified components both grouped oils into three clusters which corresponding three transitional chemotype:carophyllene oxide/cis,cis,cis-7,10,13-hexadecatrienal,carophyllene oxide/ carophyllene/deltacyclene and carophyllene oxide/3H-3a,7-methanoazulene,2,4,5,6,7,8-hexahydro- 1,4,9,9,-tetramethyl.No significant differences in chemical constituents of essential oils were observed among populations in different habitats.The similarities and also the differences in their chemical compositions were coexisting.The antibacterial effect of essential oil was evaluated preliminary.It showed stronger antibacterial activity against Bacillus subtilis at the concentration of 10 mg/ml comparing with Penicillin.It also presented antibacterial activity against Escherichia coli at the concentration of 10 mg/ml.However,no antibacterial activity was observed against Staphylococcus aureus.The distribution of Saussurea DC.in Gansu province was studied and the summarization of the chemical and pharmacological study of this genus was investigated.This work is the first chemosystematics study based on the current results of chemical studies and the investigations of the floristic study of Saussurea DC.The results showed that the five subgenres established based on the morphological characters confirm with the division based on different chemical components and their structure.However,the main chemical components in sect. Cyathidium（Lindl.ex Royle）Ling and sect.Laguranthera（C.A.Mey.Ex Endl.） Lipsch.were guaianolide,eudesmane and pentacyclic triterpenoids while the main chemical components in sect.Saussurea were quite different in subgen.Saussurea. We needed more data about chemical components of other species in Saussurea DC. Subgen.Eriocoryne（DC.）Hook.f.and subgen.Amphilaena（Stschegl.）Lipsch.were dominated with flavonoids as their main chemical components.Especially in Subgen. Eriocoryne（DC.）Hook.f.,dominated with luteolin and apigenin（floavones）which denoted more evolutional comparing with kaempferol and quercetin（floavonols）in subgen.Amphilaena（Stschegl.）Lipsch.The centre of abundance of the two subgenres is Hengduang-Himalaya which was affected greatly by the lift of Qinghai-Tibetan Plateau in late Tertiary period and early Quaternary.Related to the results of floristic study of Saussurea DC.,we preliminarily concluded that the phylogenetic relationship in Saussurea DC.was Subgen.Eriocoryne（DC.）Hook.f.—Subgen.Amphilaena （Stschegl.）Lipsch.—Subgen.Theodorea（Cass.）Lipsch.—Subgen.Florovia（DC.） Lipsch.—Subgen Saussurea.更多还原