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题名: 几种裸子植物的古植物化学研究
作者: 赵友兴
学位类别: 博士
答辩日期: 2004
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: 周俊
关键词: 裸子植物 ; 化石 ; 华山松 ; 云南铁杉 ; 银杏 ; 水杉 ; 松型球果 ; 生物标志分子 ; 化学成分
学位专业: 植物学
中文摘要: 本论文为三年期间攻读博士学位的研究工作,对几种裸子植物化石的化学成分进行了阐述,共由五章组成。第一章详细论述了上新世华山松(Pliocone Pinus armandii)化石木及其现代对应种的化学成分,并探讨了该化石木保存可能的化学原因。第二章介绍了上新世云南铁杉(Pliocene Tsuga dumosa)化石木及其现代对应种的化学成分研究。从上述两种裸子植物化石木及其现代对应种中共分离鉴定了71个化合物,其中包括55个结构不同的和9个新的化合物。部分成分具有抗木腐真菌和大型腐生真菌的活性。已鉴定的化合物类型涉及甾体、苯基脲、二萜、三萜、芪、木脂素、菲、邻苯二甲酸酯、甘油酸酯、黄酮和酚性成分。第三章对白垩纪银杏(Cretaceous Ginkgo coriacea)化石的黄酮及挥发性成分进行了分析。第四章初步分析了松型球果(Early Cretoceous Pitvostrobus)和水杉化石(Miocene etasequoia glyptostroboijes)的挥发性成分。第五章对来自古植物生源的几类生物标志分子进行了综述。一、上新世和现代华山松的化学成分研究在云南龙陵煤矿褐煤中发现保存完好的上新世华山松化石木。为什么在300万年来大部分树木形成褐煤,而华山松以化石木的形式保存于褐煤中?为探讨其保存可能的化学原因,本文对上新世和现代华山松(Pinusarmandii)的化学成分进行了比较研究。1.从上新世华山松化石木中分离鉴定了17个化合物,类型主要包括甾体、脲衍生物、芪、二萜和酚性化合物等。其中有5个新化合物,分别为N,N'-bis[4-methyl-(carbamic acid methyl ester)-3-yl]-phenylurea(1),N,N'-bis[4-methyl-(carbamic acid butyl ester)-3-yll-phenylurea(2),N,N'-bis[4-methyl-(carbamic acid isobutyl ester)-3-yl]-phenylurea(3),24ζ -n-propyl-cholestan-3-one(4)和10-isopropyl-1-methyl-1,2,3,4-tetrahydro-anthracene(11)。另外采用气相色谱一质谱联用技术(GC-MS)”鉴定了32个挥发性成分。2.华山松在中国分布较广,前人已对其树叶、树皮和心材的化学成分进行了研究,鉴定了二萜、三萜、黄酮和茵类等化学成分的存在。为比较上新世华山松的成分,本文从现代华山松心材中分离鉴定了15个化合物,类型有二萜和芪类。化合物1为新化合物,鉴定为8(17),13-labdadien-16,14-olid-18-oic acid。经GC-MS分析了24个挥发性成分。3.上新世和现代华山松鉴定的共有成分有5个,为4个芪类成分和1个二萜。表明在化石中植物成分维持了一定的稳定性。所鉴定的上新世华山松化石木的化学成分中有3个化合物(N,N'-bis[4-methyl-(carbamic acid methyl ester)-3-yl]-phenylurea,3-hydroxy-5-methoxy-stilbene 和3-hydroxy-5-methoxy-bibenzyl)具有抗木腐真菌和大型腐生真菌的活性。推测上新世华山松化石木得以保存的原因之一可能是因为含有这些活性化学成分。二、上新世和现代云南铁杉的化学成分研究云南铁杉(Tsuga dumosa)在云南分布较广,其心材的化学研究还未见报道,该属部分植物的化学研究表明主要含有木脂素。本文对采自云南昌宁煤矿的上新世云南铁杉化石木及其现代对应种的化学成分进行了阐述。1.从上新世云南铁杉化石木中分离鉴定了16个化合物,类型主要包括甾体、二萜、三萜、甘油酸酯和酚性成分等。其中化合物1为新化合物,鉴定为parryin-15,16-O-isopropylidene。另外由GC-MS分析鉴定了22个挥发性成分。2,现代云南铁杉心材中分离鉴定了23个化合物,类型主要是木脂素和黄酮。其中化合物1和8为新化合物,分别鉴定为3-(4-hydroxy-3-methoxy-benzyl)-5-[2-(4-hydroxy-3-methoxy-phenyl)-3-hydroxymethyl-7-methoxy-2,3-dihydro-benzofuran-5-yl]-4-hydroxymethyl-dihydro-furan-2-one(1,命名dumosaol)和4,8-dihydroxyepipnoresinol(8)。另外采用GC-MS鉴定了12个挥发性成分。三、白垩纪银杏叶化石的化学成分分析银杏作为一种“活化石”其化石记录可追溯到侏罗纪时代,白里纪是侏罗纪银杏进化到现代银杏的重要时期。白垩纪银杏叶(Cretoceous Ginkgo coriacea)化石的化学成分分析结果显示含有以下五类主要成分:黄酮、脂肪酸、长链烷烃、邻苯二甲酸酯及酚性成分,与现代银杏(Ginkgo Biloba)的化合物类型接近,表明白至纪银杏种的次生代谢比较接近于现代银杏种。采用液相色谱-质谱联用技术(LC-MS)鉴定了两个可能的双黄酮结构。黄酮类成分的检测表明白垩纪银杏经历了较温和的沉积环境,另外白垩纪银杏中天然的驱虫剂类化合物(邻苯二甲酸酯)、抗氧化剂(黄酮和酚性成分等)以及保护蜡层(长链烷烃和脂肪酸)可能为其保存起了重要作用。四、”松型球果和水杉化石的化学成分分析对中白至纪松型球果(Early cretaceous Pityostrobus)和中新世水杉(Miocene etasequoia glyPtostroboides)化石的挥发性成分进行了GC-MS分析,分别鉴定了19和51个化合物,并检测到了一些标志裸子植物的化合物。对水杉化石和沉积岩层中成分进行了比较分析。五、古环境中的生物标志分子(综述)本文主要对古环境中的甾体和萜类(倍半萜、二萜、三萜)及其可能的转化途径进行综述。
英文摘要: The thesis mainly contains five chapters, in which the chemical constituents of several plant fossils, Pinus armandii, Tsuga dumosa, Ginkgo coriacea, Metasequoia glyptostroboides et al. have been investigated. Seventy-one compounds including nine new compounds were isolated and identified from Pliocene Pinus armandii and Tsuga dumosa and their extant genera. These compounds covered steroids, phenylurea derivatives, diterpenoids, triterpenoids, stilbenoids, lignans, anthracene, phthalate, flavanones and aromatic derivatives. Some compounds from Pliocene Pinus armandii showed anti-wood destroying fungi and anti-saprophytic macrofungi bioactivity. 1. Chemical constituents from Pliocene and extant Pinus armandii Some lignified wood of Pinus armandii were found in an open coalmine at Longling of Yunnan Province, China. Why have most woods become brown coal while this piece of Pinus armandii retained as lignified wood form under identical external conditions? The preservation of lignified wood may lie in the characteristic difference of these ancient plants. Here we carried out the phytochemical investigation on lignified wood of Pliocene Pinus armandii and its extant genera in order to probe their organic constituents and the chemical reasons for its long-termed preservation. Seventeen compounds including five new compounds elucidated as N, N'-bis [4-methyl-(carbamic acid methyl ester)-3-yl]-phenylurea (1), N, N'-bis [4-methyl-(carbamic acid butyl ester)-3-yl]-phenylurea (2), N, N'-bis [4-methyl -(carbamic acid isobutyl ester)-3-yl]-phenylurea (3), 24 ξ -n-propyl-cholestan-3-one (4) and 10-isopropyl-l-methyl-l, 2, 3, 4- tetrahydro-anthracene (11) were isolated and identified from the lignified wood of Pliocene Pinus armandii. These compounds included steroids, phenylurea derivatives, diterpenoids, stilbenoids and aromatic derivatives. Moreover, thirty-two constituents were detected from the volatile extract of Pliocene Pinus armandii by gas chromatography-mass spectrometry (GC-MS) analysis. Pinus armandii is widely distributed in China. Previous chemical investigation of the leaves, bark and heartwood of Pinus armandii led to the isolation of three types of natural products diterpenoids, triterpenoids and stilbenoids. In order to compare the constituents with those from Pliocene Pinus armandii, this thesis described the isolation and identification of fifteen compounds including diterpenoids and stilbenoids from the heartwood of Pinus armandii. Compound 1, a new natural product, was elucidated as 8 (17), 13-labdadien-16, 14-olid-18-oic acid. Twenty-four constituents were detected from the volatile extract of the heartwood of Pinus armandii by GC-MS analysis. Five compounds including four stilbene analogues and one diterpene existed in both extant and the lignified wood of Pliocene Pinus armandii, indicating a phytochemical fidelity between fossil and extant genera. Three . compounds, N, N'-bis [4-methyl-(carbamic acid methyl ester)-3-yl]-phenylurea, 3-hydroxy-5-methoxy-stilbene and 3-hydroxy-5- methoxy-bibenzyl identified from the lignified wood of Pliocene Pinus armandii showed significant bioactivity against wood-destroying fungi and saprophytic macrofungi. The chemical reason for the preservation of the lignified wood of Pliocene Pinus armandii may directly linked to the presence of these active constituents. 2. Chemical constituents from Pliocene and extant Tsuga dumosa Some lignified wood of Tsuga dumosa were found in an open coalmine in Changning of Yunnan Province, China. Here we carried out the phytochemical investigation on lignified wood of Pliocene Tsuga dumosa and its extant genera in order to compare their organic constituents. Sixteen compounds including a new one elucidated as parryin-15, 16-0-isopropylidene (1) were isolated and identified from the lignified wood of Pliocene Tsuga dumosa. These compounds covered steroids, diterpenoids, triterpenoids, phthalates and aromatic derivatives. Moveover, twenty-two constituents were detected from the volatile extract of Pliocene Pinus armandii by GC-MS analysis. Tsuga dumosa is an economically important conifer indigenous to the Yunnan Province of China. Sesquilignans and lignans from this genus have been reported, previously. This thesis described the isolation and identification of twenty-three compounds including lignans and flavonoids from the heartwood of Tsuga dumosa. Two new compounds were elucidated as 3-(4-hydroxy-3-methoxy-benzyl)-5-[2-(4-hydroxy-3-methoxy-phenyl)-3-hydro xymethyl-7-methoxy-2,3-dihydro-benzofuran-5-yl]-4-hydroxymethyl-dihydro-furan-2-one (1) and 8-dihydroxyepipnoresinol (8) on the base of spectroscopic evidence. Twelve constituents were detected from the volatile extract of the heartwood of Tsuga dumosa by GC-MS analysis. 3. Chemical analysis of Cretaceous fossil leaves Ginkgo coriacea Ginkgo as a 'living fossil' has existed since the early Jurassic period about 170 million years ago. The following Cretaceous age (about 120 million years) is a crucial period during which the Jurassic type Ginkgo species evolved into the modern ovulate organs. Therefore, the study of Cretaceous Ginkgo, bridging the gap between Jurassic and present Ginkgo spp., is a very important link for understanding its evolution of morphology and secondary metabolism. The phytochemical investigation on Cretaceous leaves Ginkgo coriacea led to the detection of a group of natural flavonoids and other volatile including fatty acids, long chain alkyl, phthalates and phenolic compounds by GC-MS analysis. The similar types chemical constituents discovered in these two species of Ginkgo suggested that the secondary metabolism of extant Ginkgo biloba is closed to that of Cretaceous species. Two biflavonoid structures were proposed by liquid chromatography-mass spectrometry (LC-MS). The detection of flavonoids suggested that these leaves of Ginkgo coriacea underwent a mild post-depositional environment during their fossilization. This appears to be the oldest occurrence of flavonoids in plant fossils. The remaining natural products may be one of important reasons that the leaves of Cretaceous Ginkgo coriacea have been preserved morphologically in fossilization. 4. Analysis of volatiles from early Cretaceous seed cone of Pityostrobus and Miocene leaves of Metasequoia glyptostroboides 51 compounds from Miocene Metasequoia glyptostroboides and 19 from early Cretaceous Pityostrobus were detected from their volatile extracts by GC-MS analysis. From these compounds, some, such as abietane diterpenoid and retene, were saved as biomarkers derived from gymnosperm plants. Comparison of chemical constituents from fossil Metasequoia glyptostroboides and sediments showed there were some long chain lipids as n-alkyl saved in fossil and non-detected in sediments, though common compounds were detected in two samples. 5. Biomarkers from paleoenvironment Two major biomarkers, steroids and terpenoids (sesquiterpenoid, diterpenoid and triterpenoid), from paleoenvironment were summarized in this thesis. Possible diagenetic pathways of these biomarkers were reviewed.
语种: 中文
内容类型: 学位论文
URI标识: http://ir.kib.ac.cn/handle/151853/720
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几种裸子植物的古植物化学研究.赵友兴[d].中国科学院昆明植物研究所,2004.20-25
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