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KIB OpenIR  > 昆明植物所硕博研究生毕业学位论文  > 学位论文
题名: 五种百合科药用植物的甾体皂甙
作者: 杨庆雄
学位类别: 博士
答辩日期: 1999
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: 百合科 ; 药用植物 ; 甾体皂甙
学位专业: 植物学
中文摘要: 本论文研究了五种百合科药用植物的甾体皂甙成分,共包括六部分:第一章:点花黄精(Polygonatum punctatum)中的甾体皂甙成分:黄精属是百合科黄精族中典型的类群,药用植物较多。点花黄精在滇东南有分布,民间用来治疗肿毒疔疮,其化学成分未见有报导。从其根状茎中分离得到9个甾体皂甙和一个甾醇甙,结构分别为:(23S,25R)-spirost-5-ene-3β,23-diol 3-O-[α-L-rhamnopyranosyl (1→4)-β-D-glucopyranosyl]-23-O-α-L-arabinopyranoside (1), (23S,25R)-spirost-5-ene-3β,23-diol 3-O-[-α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl]- 23-O-(2-O-acetyl)α-L-arabinopyranoside (2), (23S,25R)-spirost-5-ene-3β,23-diol 3-O-[α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl] -23-O-(3-O-acetyl)-α-L-arabinopyranoside (3), (23S,25R)-spirost-5-ene-3β,23-diol 3-O-[α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl] -23-O-(4-O-acetyl)-α-L-arabinopyranoside (4), 3β, 16β, 22, 23-tetrahydroxy-5-ene- cholestanol 3-O-α-L-rhamnopyranosyl(1→2)[α-L-rhamnopyranosyl (1→4)] β-D-glucopyranoside (10), diosgenin 3-O-α-L-rhamnopyranosyl(1→2)[α-L-rhamnopyranosyl(1→4)]-β-D-glucoppyranoside (5, dioscin). 26-O-β-D-glucopyranosyl-3β,22ξ, 26-dihydroxy-furost-5-ene 3-O-α-L-rhamnopyranosyl(1→2)[α-L-rhamnopyranosyl(1→4)]-β-D-glucopyranoside (6, protodioscin), diosgenin 3-O-α-L-rhamnopyranosyl(1→2)[α-L-arabinofuranosyl(1→4)]-β-D-glucopyranoside (7, Pa), diosgenin 3-O-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranoside (8, prosapogenin A of dioscin), 26-O-β-D-glucopyranosyl-3β,22ξ,26-trihydroxy-furost-5-ene 3-O-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranoside (9, proto-type of prosapogenin A of dioscin)其中文版(1)-(4)和(10)为新化合物,分别命名为点花黄精甙A-E(Polypunctatoside A-E)。对点花黄精中的甾体皂甙的体外细胞毒活性进行了初步评价,发现点花黄精甙B及dioscin对HL-60,7901,A549,KB和HeLa等肿瘤细胞株均有较为显著的活性。选择量较大的dioscin进行了小鼠体内抗肿瘤活性实验,结果表明dioscin在体内能显著抑制小鼠肉瘤S180和小鼠肝癌HAC的生长,抑制率分别为35.3~63.5%(剂量:12.63~25.27mg/kg/d)和45.7~59.6%(剂量:12.63~25.27mg/kg/d)。以甾体皂甙为标识化合物,讨论了黄精属植物的化学分类学。第二章:云南开口箭(Tupistra yunnanensis)中的甾体皂甙成分:开口箭属在百合科中位于铃兰族内,属于较原始类群。该属植物富含甾体皂甙,有的种还含有强心甙。云南开口箭在云南地区用为中药心不干的代用品,用于治疗风湿骨痛、跌打损伤、骨折等,其化学面妥未见报导。从其根状茎中分离得十七个甾体皂甙和皂甙元,结构分别为:25(27)-en-spirost-1β,2β,3β,4β,5β-hexaol(1, Δ~(25(27))-pentologenin), 25(S)-spirost-1β,3β,4β,5β-tetraol (2, Convallagenin B), 1β, 2β, 3β, 4β, 5β, 7α-25(27)-en-6-one (3), convallagenin B 3-O-α-L-arabinopyranoside (4), 25(R)-5-en-spirost-1β,3α-diol (5, Epiruscogenin), epiruscogenin 3-O-β-D-glucopyranoside (6). 1β, 3α, 24β-trihydroxy-spirost-5,25(27)-diene 3-O-β-D-glucopyranoside (7), 25(S)-22(25)-epoxy-5-furosten-1β,3α,26-triol (8, Tupisgenin), (22S, 25S)-1α, 2β, 3α, 5α, 26-pentahydroxy-22(25)-epoxy-furostane 26-O-β-D-glucopyranoside (9), 26-O-β-D-glucopyranosyl-5, 25 (27)-dien-furost-1β, 3α, 22ξ-triol (10), 26-O-β-D-glucopyranosyl-furost-1β, 3α, 22, 26-tetrahydroxy-5-ene 3-O-β-D-glucopyranoside (11), 25(S) 26-O-β-D-glucopyranosyl-22-methoxy-1β, 3β, 4β, 5β, 26-pentol (12), 26-β-D-glucopyranosyl-22-methoxy-1α, 2β, 3α, 5α, 22ξ,26-hexaol (13), 25(S)-26-O-β-D-glucopyranosyl-22-methoxy-5β-furostan-1β, 2β, 3β, 4β, 5β, 26 -hexol (14), 26-O-β-D-glucopyranosyl-22-methoxy-1β, 2β, 3β, 4β, 5β, 7α, 22ξ-heptahydroxy-furost-25(27)-en-6-one (15), β-sitosterol (16), daucosterol (17)。化合物(4),(6),(7),(9)-(11),(13)-(15)为新化合物,分别命名为Tupistroside A-I.(1)-(15)为A环多羟基取代的甾体皂甙元.这种结构在铃兰族植物甾体皂甙成分中较为特征.第三章:大叶吊兰(Chlorophytum malayense)中的甾体皂甙成分:大叶吊兰分布于滇东南一带,民间用来治疗咳嗽、支气管管炎等。从其根状茎中分离得到四个甾体皂甙,分别为:Neohecogenin 3-O-β-D-glucopyranosyl(1→2)-[β-D-xylopyranosyl(1→3)]-β-D-glucopyranosyl(1→4) -β-D-galactopyranoside (1, Chloromaloside A), Neohecogenin 3-O-β-D-xylopyranosyl(1→3)[α-L-arabinopyranosyl (1→2)]-β-D-glucopyranosyl(1→4)-[α-L-rhamnopyranosyl (1→2)]-β-D-galactopyranoside (2, Chloromaloside C), 26-O-β-D-glucopyranosyl- 22-hydroxy-25 (S) -5α-furostan- 12-oxo-3β, 22ξ, 26-triol 3-O-β-D-glucopyranosyl(1→2)-[β-D-xylopyranosyl(1→3)]-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside (3, Chloromaloside B), 26-O-β-D-glucopyranosyl-22-hydroxy-25(S)-5α-furostan-12-oxo-3β,22ξ, 26-triol 3-O-β-D-xylopyranosyl(1→3)[α-L-arabinopyranosyl(1→2)]-β-D-glucopyranosyl(1→4)-[α-L-rhamnopyranosyl(1→2)]-β-D-galactopyranoside (4). 其中(4)为新化合物,命名为Chloromaloside E。运用HMQC, HMBC, ROESY, HMQC-TOSCY等2D-NMR技术,对Chloromaloside A, Chloromaloside B的NMR谱进行了全归属。第四章:蜘蛛抱蛋(Aspidistra elatior)中的甾体皂甙成分:蜘蛛抱蛋(Aspidistra elatior Blume)为百合科蜘蛛抱蛋属植物中分布较广并广泛栽培的一个种。云南各地农村常星散栽培于房前屋后,作为端午包棕子用的“棕巴叶“,民间常用其根状茎入药,有止血、镇痛和消炎等作用。该属植物富含甾体化合物,本种的化学成分亦已多有研究。从云南省永善县栽培的蜘蛛抱蛋根状茎中分离得到八个甾体皂甙及皂甙元,结构分别为:(25S)-3βhydroxy-spirost-5-ene 3-O-β-D-glucopyranosyl(1→2)[β-D-xylopyranosyl(1→3)]-β-D-glucopyranosyl (1→4)-β-D-galactopyranoside (1), 26-O-β-D-glucopyranosyl-furost-3β,22ξ,26-trihydroxy-5-ene 3-O-β-D-glucopyranosyl (1→2)[β-D-xylopyranosyl(1→3)]-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside (2), 26-β-D-glucopyranosyl-22-methoxy-1α, 2β, 3α, 5α, 22ξ,26-hexaol (3, Tupistroside G), 1β,2β,3β,4β,5β-pentahydroxy-spirost-25(27)-ene 5-O-β-D-glucopyranoside (4), (25S)-1β,2β,3β,4β,5β-pentahydroxy-spirostan 5-O-β-D-glucopyranoside (5), 25(S)-26-O-β-D-glucopyranosyl-22-methoxy-5β-furostan-1β,2β,3β,4β,5β,26-hexol (6, Tupistroside H), (25S)-spirost-1β,2β,3β,4β,5β-pentol (7, neopentrogenin), (25S) 1β,2β,3β,4β,5β-pentahydroxy-spirostan-2-yl sulfate (8).化合物4为新的甾体皂甙,命名为蜘蛛抱蛋甙A (aspidoside A), 8为一新的甾体皂甙元硫酸盐。(1-3), (6)均为首次从该属植物中分离得到。从云南省永善县产的蜘蛛抱蛋中未发现薯蓣皂甙元的配糖体,得率最高的是蜘蛛抱蛋甙的呋甾烷型原皂甙2,另一主要皂甙1为蜘蛛抱蛋甙的差相异构体,即约莫皂甙元的配糖体。似乎在该植物中,原皂甙2只转化为1而不转化为蜘蛛抱蛋甙,这一由不同居群产生的化学多态性现象似乎与该物种的分布和变异与进化有关。此外,我们从蜘蛛抱蛋中还分离到一系列pentrogenin衍生物及其配糖体,这类A环多羟基取代的甾体化合物提示了蜘蛛抱蛋属与吉祥草属、万年青属和心不干属之间密切的关系的亲缘关系。第五章:深裂竹根七(Disporopsis pernyi)中的 体皂甙成分:竹根七属为或南亚一带的特有属,分布我国长江以南及中南半岛(越南、老挝和泰国),共有4种,云南省均产。深裂竹根七有祛风湿、清热解毒国效,分布于滇中、滇东南,其化学成分未见报导。从其根状茎中分离得到七个甾体皂甙,结构分别为:smilagenin 3-O-β-D-glucopyranosyl(1→2)-β-D-glucopyranoside (1, Ys-I), smilagenin 3-O-β-D-glucopyranosyl (1→2)[β-D-glucopyranosyl (1→6)]-β-D-glucopyranoside (2), 26-O-β-D-glucopyranosyl-5β-furost-3β, 22ξ, 26-triol-3-O-β-D-glucopyranosyl(1→2)-β-D-glucopyranoside (3), 26-O-β-D-glucopyranosyl-5β-furost-3β, 22ξ, 26-triol- 3-O-β-D-glucopyranosyl(1→2)[β-D-glucopyranosyl (1→6)]-β-D-glucopyranoside (4), 3-O-β-D-glucopyranosyl(1→2)-[6-O-palmitoyl]-β-D-glucopyranoside (5), neohecogenin 3-O-β-D-glucopryanosyl(1→4)-β-D-galactopyranoside (6), 3-O-α-L-arabinopyranosyl(1→3)β-D-glucopyranosyl(1→4)-β-D-galactopyranoside (7).化合物(2)-(7)为新的甾体皂甙,分别命名为Disposide A-F。第六章:百合群植物的、甾体皂甙在百合群中的分布甾体皂甙在百合科化学分类学中的意义以及近年来百合群植物中甾体皂甙化学研究情况进行了简要介绍,着重介绍了甾体皂甙结构解析。最后对甾体皂甙化合物的生理活性研究作了较为详尽的综述。
英文摘要: The steroidal saponins of five medicinal liliaceous plants were investigated in thisthesis, and the thesis consists of six chapters:1, Steroidal saponins from Polygonatum punctatum Polygonatum punctatum Baker is distributed in the southeast of Yunnan province,China. Its rhizomes, as a crude material of "Huang-Jing", are used as the remedy topyogenic infections and funmcle. From the methanol extracts of the rhizomes of P Punctatum, ten steroidal saponins were obtained. These Saponins were identified as:(23S,25R)-spirost-5-ene-3β,23-diol 3-O-[α-L-rhamnopyranosyl (1 →4)-β-D- glucopyranosyl]-23-O-α-L-arabinopyranoside (1), (23S,25R),spirost-5-ene-3β,23-diol 3-O- [-α-L-rhamnopyranosyl(1 →4)-β-D-glucopyranosyl]- 23-O-(2-O-acetyl)-α-L-arabinopyranoside (2), (23S,25R)-spirost-5-ene-3β,23-diol 3-O-[α-L-rhamnopyranosyl( 1→4)-β-D-glucopyranosyl]-23 -0-(3 -O-acetyl)-α-L-arabinopyranoside (3),(23S,25R)-spirost-5-ene-3β,23-diol 3-O-[α-L-rhamnopyranosyl(1→4)-β-D-glucopyranosyl] -23-O-(4-O-acetyl)-α-L-arabinopyranoside (4), 3β, 16β, 22, 23-tetrahydroxy-5-ene- cholestanol 3-O-α-L- rhamnopyranosyl(1→2)[α-L-rhamnopyranosyl (l→4 )]β-D-glucopyranoside (10),diosgenin  3-O-α-L-rhamnopyranosyl(l→2)[α-L-rhamnopyranosyl(1→4)]-β-D-glucoppyranoside (5, dioscin).26-O-β-D-glucopyranosyl-3β,22ξ, 26-dihydroxy-furost-5-ene 3-O-α-L-rhamnopyranosyl(1→ 2)[α-L-rhamnopyranosyl(1→4)]-[β-D-glucopyranoside (6, protodioscin), diosgenin 3-O-α-L-rhamnopyranosyl(1→2)[α-L-arabinofuranosyl(1→4)]-β-D-glucopyranoside(7, Pa),diosgenin 3-O-α-L- rhamnopyranosyl(1→2)-β-D-glucopyranoside (8, prosapogenin A of dioscin), 26-0-β-D-glucopyranosyl-3β,22ξ,26-trihydroxy- furost-5-ene 3-O-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranoside (9, proto-type of prosapogenin A of dioscin). Among them, compounds (1)-(4) and (10) were new steroidal saponins, and named as polypunctatoside A-E. The cytotoxic activity of the isolated compounds was evaluated and it was found that polypunctatoside B and disocin had apparent cytotoxic activity towards HL-60, 7901, A549, KB and HeLa cell lines in vitro. Furthermore, dioscin inhibited the mouse sarcoma (S180) and mouse hepatic cancer (HAC) in vivo. By the Selecting steroidal saponins out as chemical maker compounds, the chemotaxonomy of Polygonatum plants was discussed. 2, Steroidal saponins from Tupistra yunnanensis Tupistra yunnanensis Wang et Tang is a liliaceous plant growing in the Yunnan province, China. It is one of the Chinese traditional medicines, and named as "Xin-Bu-Gan (心不干)". Its rhizomes are used as the remedy to stomach upset and injures. From the rhizomes of T. yunnanensis, seventeen steroidal saponins and sapogenins were yielded. The structures were identified as: 25(27)-en-spirost-lβ,2β,3β,4β,5β-hexaol (1, △~(25(27))-pentologenin), 25(S)-spirost- 1β,3β,4β,5β-tetraol (2, Convallagenin B), 1β, 2β, 3β, 4β, 5β, 7α-25(27)-en-6-one (3), convallagenin B 3-O-α-L-arabinopyranoside (4), 25(R)-5-en-spirost- 1β,3α-diol (5, Epiruscogenin),epiruscogenin 3-O-β-D-glucopyranoside (6). 1β, 3α, 24β-trihydroxy-spirost-5,25(27)-diene 3-O-β-D-glucopyranoside (7),25(S)-22(25)-epoxy-5-furosten-1β,3α,26-tri01 (8,Tupisgenin), (22S, 25S)-1α, 2β, 3α, 5α, 26-pentahydroxy-22(25)-epoxy-furostane 26-O-β-D-glucopyranoside (9), 26-O-β-D-glucopyranosyl-5, 25 (27)-dien-furost-1β,3α, 22ξ-triol (10),26-O-β-D-glucopyranosyl-furost-1β, 3α, 22, 26-pentahydroxy-5- ene 3-O-β-D-glucopyranoside (11), 25(S)26-O-β-D-glucopyranosyl-22-methoxy-lβ, 3β, 4β, 5β, 26-pentol (12), 26-β-D-glucopyranosyl-22-methoxy-lα, 2β, 3α, 5α, 22ξ,26-hexaol (13),25(S)-26-O-β-D-glucopyranosyl-22-methoxy-5β-furostan-1β, 2β,3β, 4β, 5β, 26 -hexol (14),  26-O-β-D-glucopyranosyl-22-methoxy-1β, 2β,3β,4β, 5β, 7α, 22ξ-heptahydroxy-furost-25(27)-en-6-one (15), β-sitosterol (16), Daucosterol (17). Among them, compounds (4), (6), (7), (9)-(11), (13)- (15) were new steroidal saponins, and named as tupistroside A-I.3, Steroidal saponins from Chlorophytum malayense Chlorophytum malayense is distributed in the pantropical regions, especially in the south of Yunnan province, China. The rhizomes of this plant are used as remedy to coughing, pyogenic infections and tracheitis in the Chinese folk medicine. Four steroidal saponins were obtained from the methanol extracts of its rhizomes, and identified as: Neohecogenin 3-O- β- D-glucopyranosyl( 1→ 2)- [β-D- xylopyranosyl( 1→3)]-β-D-glucopyranosyl( 1→4) -β-D-galactopyranoside (1,Chloromaloside A), Neohecogenin 3-O-β-D-xylopyranosyl( 1→3) [α-L-arabinopyranosyl (1→2)]-βD-glucopyranosyl(1→4)-[α-L-rhamnopyranosyl (1→2)]- β-D-galactopyranoside (2, Chloromaloside C), 26-O-β-D-glucopyranosyl- 22-hydroxy-25(S)-5α-furostan- 12-oxo-3β, 22ξ, 26-triol 3-O-β-D-glucopyranosyl(1→2)- [β-D-xylopyranosyl(1→3)]-β-D-glucopyranosyl(1→4)- β-D-galactopyranoside (3,Chloromaloside B), 26-O-β-D-glucopyranosyl-22-hydroxy-25(S)-5α-furostan-12- oxo-3β,22ξ, 26-triol 3-O-β-D-xylopyranosyl(1 →3)[α-L-arabinopyranosyl( 1→2)]-β-D-glucopyranosyl(1→4)-[α-L-rhamnopyranosyl(1→2)] -β-D-galactopyranoside (4). Saponin 4 was a new steroidal saponin, and named as Chloromaloside E. The NMR spectra of chloromaloside A and chloromaloside B were whole assigned with the application of HMQC, HMBC, HMQC-TOCSY and ROESY techniques. 4, Steroidal saponins from Aspidistra elatior A. elatior has been widely cultured in China. Its leaves are used to pack rice and named as "Zong-zi", a kind of traditional food in China, and its rhizomes were used in the traditional Chinese medicine, as the remedy to pyogenic infections and fractures. It was known that steroidal saponins were rich in the Aspidistra genus. From the rhizomes ofA. elatior collected in Yongshan, Yunnan province, China, eight steroidal saponins and sapogenins were yielded, and identified as: (25S)-3β-hydroxy-spirost-5- ene 3-O-β-D-glucopyranosyl(1→2)[β-D-xylopyranosyl(1→3)]-β-D-glucopyranosyl(1→4)- β-D-galactopyranoside(1),26-O- β-D-glucopyranosyl- furost-3 [3,22~,26- trihydroxy-5-ene 3-O-β-D-glucopyranosyl (1→2)[β-D-xylopyranosyl(1→3)]-β-D-glucopyranosyl( 1→4)- β-D-galactopyranoside(2),26-β-D-glucopyranosyl-22- methoxy-lα, 2β, 3α, 5α, 22ξ(3, Tupistroside G), 1β,2β,3β,4β,5β-pentahydroxy-spirost-25(27)-ene 5-O-β-D-glucopyranoside (4), (25S)-lβ,2β,3β,4β,5β-pentahydroxy-spirostan 5-O-β-D-glucopyranoside (5), 25(S)-26-O-l[3- D-glucopyranosyl-22-methoxy-513-furostan-l[3, 213, 3[3, 4[3, 5[3, 26 -hexol (6,Tupistroside H), (25S)-spirost-1β,2β,3β,4β,5β-pentol (7, neopentrogenin), (25S) 1β, 2β, 3β, 4β, 5β-pentahydroxy-spirostan-2-yl sulfate (8). 4 and 8 were new comounds from the natural source, and compounds 1, 2, 3, 6 were obtained from this genus for the first time. 5, Steroidal saponins from Disporopsis pernyi Disporopsis pernyi (Hua) Diels, a folk herb in China, is used as remedy to coughing and often as a tonic. Phytochemical investigation on its rhizomes resulted in seven steroidal saponins. The structures were identified as: smilagenin 3-O-β-D- glucopyranosyl( 1→2)-β-D-glucopyranoside (1,Ys-l), smilagenin 3-O-β-D-glucopyranosyl (1→2)[β-D-glucopyranosyl (1→6)]-β-D-glucopyranoside (2), 26-0- β-D-glucopyranosyl-5β-furost-3β. 22ξ,26-triol-3-O-β-D-glucopyranosyl(1→2)-β-D-glucopyranoside (3), 26-O-β-D-glucopyranosyl-5β-furost-3β, 22ξ, 26-triol- 3-0- β-D-glucopyranosyl(1→2)[β-D-glucopyranosyl (1→6)]-β-D-glucopyranoside (4), 3- O-β-D-glucopyranosyl( 1→2)- [6-O-palmitoyl] - β-D-glucopyranoside (5),neohecogenin 3-O-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside (6), 3-O-α-L- arabinopyranosyl( 1→3) β-D-glucopyranosyl( 1 →4)-β-D-galactopyranoside (7). Among them, compounds 2-7 were new steroidal saponins, and named as disposide A-F. 6, Review The advances in the steroidal saponins of lilicaeous plants were reviewed, including the chemistry and biological activities of steroidal saponins, and chemotaxonomy of some genera of liliaceae.
语种: 中文
内容类型: 学位论文
URI标识: http://ir.kib.ac.cn/handle/151853/496
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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