三种杉科植物及黄棉木的化学与活性成分研究
其他题名Chemical and Bioactive Constituents of Three Taxodiaceae Plants and Metadina Trichotma
张玉梅
学位类型博士
导师谭宁华
2005
学位授予单位中国科学院昆明植物研究所
学位授予地点中国科学院昆明植物研究所
学位专业植物学
关键词杉科 北美红杉 墨西哥落羽杉 池杉 茜草科 黄棉木 化学成分 生物活性成分
摘要本论文由三部分组成:第一部分介绍了杉科植物北美红杉(SeqltoiasempervirensEndl.)·墨西哥落羽杉(Taxodiumm:IcronalumTenore)·池杉(TatojiumascendensBrongn)和茜草科植物黄棉木(Metadinatrichotoma(2011.Et.Mor.)Bakn.F.)的化学成分研究。从4种植物中共分离鉴定了62个化合物(已减去7个重复化合物),其中23个为新化合物,42个为首次报道。杉科植物的化合物类型主要涉及降木脂素、新木脂素及其昔、黄酮及其昔、双黄酮、蹂质、倍半菇及其营等。北美红杉中得到的北美红杉素A(SequosempervirinA,1)为第一次发现的具有C6-C3-CZ-C6螺环结构的新颖降木脂素,在TL(2004,45:4319)上发表后即被NPR[2004.21(4):H14]列为热点化合物·茜草科植物黄棉木的化合物类型主要涉及乌索酸型三菇及其营、C一27降齐墩果酸型三菇昔和A环开裂的三菇营元等。降木脂素为北美红杉的主要特征成分,池杉中也含有;黄酮及其营为墨西哥落羽杉的主要特征成分;新木脂素及其营为池杉的主要特征成分,墨西哥落羽杉中也含有;三菇及其营为黄棉木的主要特征成分。我们还推测了北美红杉中系列降木脂素(化合物2-10)的相互转化机理;并根据莽草酸途径推测了北美红杉中化合物1-3、8和14的生物合成途径。第二部分介绍了巧种杉科植物的粗提物、3种杉科植物和茜草科植物黄棉木的粗分段部位及所得部分化合物在8个体外活性筛选模型上的活性筛选结果。目前已经从111个待筛样品中发现134个/次活性样品,其中活性化合物12个/次。杉科植物的活性主要表现在抗骨质疏松模型CA下B和抗肿瘤模型CCLT上,在抗真菌模型YNG和抗肿瘤模型CDC25上也具有一定活性。特别是从墨西哥落羽杉中分离得到的3个双黄酮[Amentoflavone(1)、Podocarpusflavone(2)和4,7-Dimethylamentoflavone(3)l,活性实验结果表明它们是组织蛋白酶B较强的新型天然抑制剂,其ICS。值分别为1.75、1.68、o,55卜LM,基于计算机辅助的作用机理和虚拟筛选研究正在进行,目前己经证明活性实验结果与理论计算一致。这3个双黄酮在抗肿瘤模型CCLT上也表现出一定活性。茜草科植物黄棉木的活性主要表现在抗骨质疏松模型CAT-B上,实验结果还初步表明黄棉木中的三菇昔类化合物在抗肿瘤模型CCLT上有活性,其它活性研究正在进行中。第三部分综述了20世纪50年代以来杉科植物化学与活性成分的研究进展。以上研究结果拓宽了杉科植物的化学和活性成分研究,为该科植物的化学分类学提供了一定的实验依据。首次对茜草科植物黄棉木的系统化学与活性研究,为其资源的开发利用提供了一定的实验依据。论文三部分工作具体介绍如下:第一章为三种杉科植物和茜草科植物黄棉木的化学成分研究,重点介绍62个化合物(已减去7个重复化合物)的分离及其结构鉴定。第一节为杉科植物北美红杉(S.sempervirens)的化学成分研究。我们对采自昆明植物园的北美红杉枝仆卜进行了较系统化学成分研究,从中分离鉴定了19个化合物,其中降木脂素为其主要特征成分。北美红杉素A-G(seqLlosempervirinA-G,1-7)、北美红杉醇A-B(SequosempervirolA-B,11-12)、北美红杉普A(SequosempervirosideA,13)和莽草酸乙酷(ShikimicacidEtester,14)为11个新化合物。化合物10-Nonacosonol(15)、胡萝卜营(16)、Q-D-目比喃果糖乙昔(17)、Q-D-毗喃葡萄糖乙营(18)和p-D·毗喃葡萄糖乙昔(19)为首次从北美红杉中分离得到。我们还推测了北美红杉中系列降木脂素(化合物2一10)的相互转化机理;还根据莽草酸途径推测了化合物1-3、8和14的生物合成途径。第二节为杉科植物墨西哥落羽杉(厂mllcronatu)的化学成分研究。我们对采自昆明植物园的墨西哥落羽杉枝叶进行了较系统的化学成分研究,从中分离鉴定了15个化合物,其中黄酮及其昔为其主要特征成分。新化合物为墨西哥落羽杉昔A(axomucrosideA,12)。化合物Amentoflavone(1),4·,7-Di件ethylamentofl"Vone(3),梅}皮素-3'-甲氧基-3-0-p-D-,比喃半乳糖昔(Quetcetin3,-methoxy-3-O-日-D-galactopyranoside,4),梅(皮素(Quercetin,5),棚皮素-3'-甲氧基-3-0-Q-L-毗喃阿拉伯糖普(Quercetin3,-meth0Xy-3-O-日-D-arabin叩yran0Side,6),懈皮素-3,-甲氧基-3·口-"-L-吠喃阿拉伯糖营(QLlercetin3-methoxy-3-。-。-L-。robin。九ronoside,7),柳}皮素-3-。-Q-L-吠喃阿拉伯糖昔(viculorin,8),棚皮素-3-o.p-D-毗喃半乳糖营(Quercetin3-。-日-D-galactopyranoside·9),(7'S·8,S)·4·7'-Ep0Xy-3·3,-dimeth0Xy-4·9·3'·4',9,·lignanepentol-4,-O-p-D-glucopyranoside(10)·(7,S,8'S)-3,3,-Dimethoxy-9,4,,9,-trihydroxy-4,8,-oxyneoligllan-7,-O-日-D-glucopyranside(11),莽草酸甲酷(shikimicacidMeester,13),1一TI.idecanol(14)和p一谷形醇(15)为首次从墨西哥落羽杉中分离得到。第三节为杉科植物池杉(笠ascel?des)的化学成分研究。我们对采自昆明植物园水生区的池杉枝进行了较系统的化学成分研究,从中分离鉴定了16个化合物,其中新木脂素及其营为其主要特征成分。池杉素A(TaxodascendinA,1),池杉营A(TaxodascenosideA,6),池杉素B(TaxodascendinB,10),池杉素c(TaxodascendinC,n)为4个新化合物。化合物北美红杉素B(2),Agatllaresillol(3),Cryptoresinol(4),(7,S,8,S)-4,7,-Epoxy-3,3,-dimethoxy-4,9,3,,4,,9,-lignanepentol(5),(7,S,8,S)-4,7,-Epoxy-3,3,-dimethoxy-409,3,,4,,9,-lignanepentol-4,-0-日-D-glucopyranside(7),(7,S,8'S)-9,4,,9,-TI-ihydroxy-3,3,-dimethoxy-4,8,-oxyneolignan-7,-0-旦-D-glucopyranside(8),Epicatechin(9),e,?t-16日-Katlranol(12),3,4-Dimethox"henyl-日-D-glucoside(13),3,4,5-Trimethoxypllenyl-日-D-glucoside(14),胡萝卜昔(15)和Q-D-吠喃果糖甲普(16)为首次从墨西哥落羽杉中分离得到。第四节为茜草科植物黄棉木啊tlic/choto],Za)的化学成分研究。我们对采自西双版纳的黄棉木树皮进行了较系统的化学成分研究,.从中分离鉴定了19个化合物,其中三菇及其昔为黄棉木的主要特征成分。黄棉木素A(MetatricllotinA,2),黄棉木素B(MetatricllotinB,3),黄棉木昔A(MetatrichosideA,8),黄棉木昔B(MetatrichosideB,9),黄棉木昔C(MetatrichosideC,11),黄棉木着D(MetatrichosideD,12)和黄棉木营E(Metatl-icllosideE,13)为7个新化合物。化合物3,4-seco-4(23)-stictene-3,22a-diol(1),Quinovicacid-3-。-p-D-quinovopyranoside(4),Quinovicacid-3-O-日-D-glucopyranoside(5),Quinovicacid-3-O-p-D-quinovopyranosyl-28-O-p-D-glucopyranoside(6),Quinovicacid-3-O-p-D-glucopyranosyl-28-O-p-D-glucopyranoside(7),27-Nor-oleanolicacid,3-O-p-D-quinovopyranosyl-28-O-日-D-glucopyranoside(10),Scopoletin(14),(ZR,35)-3,5,7,3,,4'-Pentahydroxyflavan(15),(25,3R)-3,5,7,3,,4,-Pentallydroxy且avan(16),3-(4,-Hydroxyphenyl)-2-propenoicacid(17),3,4-Dthydroxybenzaldehyde(18)和p一谷浴醇(19)为首次从黄棉木中分离得到。第二章为杉科植物和茜草科植物黄棉木的活性成分研究。主要介绍15种杉科植物的粗提物、3种杉科植物和茜草科植物黄棉木的粗分段部位及所得部分化合物在8个体外筛选模型上(抗骨质疏松模型CAT-B和CAll、抗肿瘤模型CDC25和ccLT、抗真菌模型YNG、溶血栓模型PAI、抗黑色素沉积模型Ts以及代谢模型PPI)的活性筛选结果。
其他摘要The thesis is composed of three parts:In the first part, we studied on the chemical constituents of three Taxodiaceae plants (Sequoia sempeiyirens Endl, Taxodiwn muavnatwn Tenore, Taxodium ascendens Brongn) and Rubiaceae plant Metadina irichotoma (Zoll. Et Mor.) Bakn. T. E. Sixty two compounds have been obtained and identified from these plants, in which twenty three compounds were new and forty two compounds were reported for the first time in these plants. Cornpounds from these Taxodiaceae plants mainly belong to norlignans, neolignans, neolignan glucosides, flavones, fiavone glucosides, biflavones, tannings, sesquiterpenes, sesquiterpene glucosides and so on. Sequosemperverin A (1) isolated from S sempenirens was the first naturally occurring norlignan containing one spirocycle with C6 (cyclohexane)-C2-C3-C6 skeleton, which was reported by NPR (2004, 21 (4): H14) as one hot off the press compound after its publication on TL (2004, 45: 4319). Compounds from M tricholoma mainly belong to triterpenes, triterpene glucosides and so on. Results indicated that norlignans were the characteristic constituents of £ sempeiyirens and also obtained from T. ascendens; flavones and its glucosides were the characteristic constituents of T. muavnatwn; neolignans and its glucosides were the characteristic constituents of T. ascendens and also obtained from T. muavnatwn; and triterpenes and its glucosides were the characteristic constituents of hi trichotoma. We also deduced Hie possible conversion mechanism of norlignans 2-10 and biosynthesis pathway of compounds 1-3, 8, 14 from SI sempennrens.The second part dealt with studies on the bioactivities of extracts from 15 Taxodiaceae plants, fractions and some compounds from S. sempeiyirens, T. mucmnatum, T. ascendens and M. tiichotoma. One hundiied and eleven samples were tested on anti-osteoporosis (CAT-B and CA II), anti-tumor (CDC25 and CCLT), anti-fungus (YNG), anti-melanogenesis (TS), anti-toombus (PAI) and metabolism (PPl) bioassays. Up to now, one luuidred and thirty four bioactive samples have been found, in which 12 were compounds. Results of Taxodiaceae plants mainly showed some bioactivities on anti-osteoporosis (CAT-B), anti-cancer (CCLT), anti-fungus (YNG) and anti-tumor (CDC25) bioassays. Biflavones amentoflavone (1), Podocarpusflavone (2) and 4', 7 -Dimethylamentoflavone (3) from T. mucronatum were found to be a potential new type of natural inhibitors on cathepsin B with IQo values of 1.75, 1.68 and 0.55jaM, which also showed anti-cancer activity on CCLT assay (A549). Two triterpene glucosides Quinovic acid -3-O-P-D-quinovopyranoside (4) and Quinovic acid-3-O-p-D- quinovopyranosyl-28-O-P-D-glucopyranoside (6) from M. trichotoma have been found to show anti-cancer activity on CCLT assay (A549) with IC50 values of 5.33,4.81 u.g/ml.The third part reviewed the chemical and bioactive constituents of Taxodiaceae plants since 1950's. Up to now, over 370 compounds have been isolated and identified from Taxodiaceae plants which mainly belong to terpenoids, flavones, lignans and sterols. And anti-fungus, antiulcer, antitumor, anti-inflammatory, antioxidant, antifeedant and anti-bacteria constituents from Taxodiaceae plants also have been reported.In one word, extensive investigations on chemical and active constituents of 5! sempervirens, T. mucwnalum, T. ascendens and M. tiicliotoma have expanded their researches and provided more evidences for chemical taxonomy of Taxodiaceae plants and utilization for these plants.
页数118
语种中文
文献类型学位论文
条目标识符http://ir.kib.ac.cn/handle/151853/756
专题昆明植物所硕博研究生毕业学位论文
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张玉梅. 三种杉科植物及黄棉木的化学与活性成分研究[D]. 中国科学院昆明植物研究所. 中国科学院昆明植物研究所,2005.
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