竹叶菜、菊叶薯蓣和小花盾叶薯蓣的化学成分与抗癌活性研究
其他题名Constituents from Smilacina atropurpurea, Dioscorea composita and Dioscorea parviflora, and the Inhibitory Activity of S. atropurpurea on K562 cell
杨顺丽
学位类型硕士
导师刘锡葵
2004
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
关键词竹叶菜 菊叶薯蓣 小花盾叶薯蓣 抗癌活性 甾体皂苷 核苷 二苯丙烷类化合物
摘要甾体皂苷类化合物是一类广泛存在于植物中的重要植物次生代谢产物,具有抗炎、抗霉菌、抗癌、降血糖和抑精等广泛的生理活性,其苷元同时也是合成用体激素药物的重要原料。本论文对民间野生食用植物竹叶菜[高大鹿药(Smilacina atropurea(Franch.)Wang et Tang)]、菊叶薯蓣(Dioscorea con,ositaHemsl)和小花盾叶薯蓣(D ioscorea paryiflra C.T.Ting.)等三种富含甾体皂苷植物的化学成分进行了研究,应用大孔树脂、硅胶、反向硅胶(RP-18)等分离材料和Uv、IR、ZD-NMR、MS、X-ray等现代波谱分析及化学的方法,从上述三种植物中分离鉴定了38个化合物,包括核苷、发;甾体皂苷、二苯丙烷、植物甾醇等化合物,发现新化合物8个,并对竹叶菜中主要甾体皂苷化合物的K562活性进行了筛选。本论文由四个部分组成:第一部分:竹叶菜化学成分及其抗癌活性研究竹叶菜[高大鹿药(Sn:ilacina atropurPurea(FraJlcll.)Wang et Tang)]系百合科鹿药属多年生草本植物,在四川东南部、云南西北部及西藏地区的藏族、傈僳族和纳西族将其幼嫩茎叶长期作为野生蔬菜食用。从竹叶菜的甲醇提取物中分离鉴定了14个化合物,分别鉴定为胸腺嘧啶脱氧核苷(thymidine,l)、腺嘌呤核苷(adenosine,2)、2'-脱氧腺苷(2'-deoxyadenosine,3)、薯蓣苷元3-O-α-L-吡喃鼠李糖基-(1→3)-「6-O-棕榈酸酯基]-O-β-D-吡喃半乳糖苷{diosgein3-O-α-L-thanmopyranesyl-(1→3)-[6-O-palmitoxyl]-O-β-D-galactopyranoside,4,smilacinosideA}、薯蓣苷元3-O-a-L-吡喃鼠李糖基-(1→2)-O-β-D-吡喃半乳糖苷{diosgenin3-O-a-L-rhamnopyranosyl-(1→2)-O-β-D-galactopyr anoside,5,smilacinosideB}、26-O-β-D-吡喃葡萄糖基-(25R)-呋甾-5-烯-3β,22ζ,26-三醇3-O-a-L-吡喃鼠李糖基-(1→2>β-D-吡喃甘露糖苷{26-O-β-D-glucopyranosyl-(25R)-furost-5-en-3β,22α,26-triol3-O-a-L‘thamnop,anosyl-(1→2)}-β-D-galactopyranoside,6,smilacinosideC}、26-O-β-D-吡喃葡萄糖基-22-甲氧基-(25R)-呋甾-5-烯-3β,26-二醇3-O-a-L吡喃鼠李糖基-(1→2)-β-D-吡喃半乳糖苷{26-O-β-D-glucopyranosyl-22-OCH3一(25R)-furost-5-en-3β,26-diol3-O-a-L-rhamnopyranosyl-(1→2)-β-D-galactopyranoside,7,smilacinosideD}、薯蓣皂苷元3-O-β-D-吡喃葡萄糖基-(1→2)-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷{diosgenin3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyran0Syl-(1→4)-β-D-galac-topyranoside,8,玉簪苷D,funkiosideD}、薯蓣皂苷元3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃木糖基-(1→3)]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷{diosgenin3-O-β-D-glucopyranosyl-[β-Dxyloyranosyl-(1→3)]-β-D-glucopyran-osyl-(1→4)β-D-galactopyranoside,9,蜘蛛抱蛋皂苷,aspidistrin}、26-O-β-D-吡喃葡萄糖基-22-甲氧基-(25R)-呋甾-5-烯-3β,26-二醇3-O-β-D-吡喃葡萄糖基-(1→2)-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷{26-O-β-D-glucopranosyl22-OCH3-(25R)-furost-5-en-3β,26-diol3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)β-D-galactopyranoside,10}、β-胡萝卜甙(daucosterol,n)、三十烷醇(n- triacoatanol,12)、棕榈酸(palmiticacid,13)、新替告皂苷元3-O-β-D-吡喃葡萄糖基-(1→2)-[β-D-吡喃木糖基-(1→3)]-β-D-吡喃葡萄糖基-(1→4)-β-D-吡喃半乳糖苷{nitigogenin3-O-β-D-gtucopyranosyl-[β-D-xylopyranosyl-(1→3)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside,14,鹭鸶兰苷A(d iuranthosideA)}。其中1、2、3为核苷类化合物,化合物3系首次从植物中分离得到;4、5、6、7为新的篷体皂苷化合物,分别命名为竹叶菜苷A、B、c、D(smilocinosideA,B,c,D),14从根茎中分离得到。经对化合物4、5、6、7、8、9及总提取物的体外K562细胞活性筛选,发现化合物5,8和9对K562细胞生长有显著抑制作用,其ICS。分别为1 .09、2.93、0.47μg/ml。另外对竹叶菜新鲜茎叶和根与干燥茎叶的化学成分进行比较,发现新鲜茎叶与干燥茎叶的化学成分基本相同,而根茎的化学成分与茎叶相差较大,仅含少量出体皂苷,明显与茎叶不同。第二部分菊叶薯蓣化学成分研究菊叶薯蓣(Dioscorea composita Hemsl)属薯蓣科薯蓣属多年生高大藤本植物,原产于墨西哥,是生产合成甾体激素药物原料的重要植物原料之一。我国1978年自墨西哥引种,在西双版纳等热带地区进行栽培。从栽培于西双版纳的菊叶薯蓣甲醇提取物中分离鉴定了11个化合物,分别鉴定为1,3-二-(2-羟基-4-甲氧基苯基)丙烷[1,3-bis-(2-ydroxy-4-methoxyphenyl)-propane,11、l,3-二-(2,4-二羟基苯基)丙烷[1,3-bis-(2,4-dihydroxyphenyl)propane,2]、1-(2'-羟基-4'-O-β-D-吡喃葡萄糖基苯基)-3-(2″,4″-二羟基苯基)丙烷[1-(2'-hydroxy-4'-O-β-D-glucopyranosyphenyl)3-(2″,4″-dihydroxyphenyl)propane,3]、薯蓣皂苷前皂苷元A(P ros即ogenin A of dioscin,4)、薯蓣皂苷(dioscin,5)、穗菝葜甾苷(asperin,6)、甲基原薯蓣皂苷(methyl protodioscin,7)、原薯蓣皂苷(protodioscin,8)、甲基原穗菝葜甾苷(methyl asperoside,9)、原穗菝葜甾苷(asperoside,10)、棕榈酸(paimitic acid,11)。其中化合物6,9和10系首次从菊叶薯蓣中分离得到:化合物7和9,为8和10的甲氧基转化产物,化合物1、2、3为新的二苯丙烷类化合物。第三部分小花盾叶薯蓣化学成分研究小花盾叶薯蓣(D ioscorea parviflora C.T.Tinb.)(苦良姜),为薯蓣科(Dioscoreaceae)薯蓣属(D ioscorea L.)根茎组(Sect.Stenophora Uline)多年生草本攀缘植物,主产于云南,为我国特有种,是生产合成甾体激素药物原料薯蓣皂苷元(diosgenin)的重要植物原料。从小花盾叶薯蓣乙醇提取物的硅藻土乙醇洗脱部分分离得到12个结晶状化合物,分别鉴定为:去酰百合皂苷(deacylbrownioside,1)、薯蓣皂苷元-双葡萄糖苷(diosgenin-diglucoside,2)、前薯蓣皂苷A(P rosapogenin A of dioscin,3)、薯蓣皂苷(dioscin,4)、三角蓣皂苷宁(deltonii,5)、三角薯蓣皂苷(deitoside,6)、甲基三角薯蓣皂苷(methyl deltoside,7)、薯蓣皂苷元-3-O-β-D-吡喃葡萄糖基-(l→3)-β-D-吡喃葡萄糖基-(1→4)-[α-L-吡喃鼠李糖基-(1→2)]-β-D-吡喃葡萄糖昔{diosgenin3-O-β-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl-(1→4)-[α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranoside,8}、小花盾叶薯蓣甙(parvifloside,9)、甲基小花盾叶薯蓣甙(methyl parvifloside,10)、薯蓣皂苷元(diosgenin,11)、β-谷甾醇和豆甾醇(β-sitosterol,12,&stigmasterol,13)。其中1、2、4、7系首次从小花盾叶薯蓣中分离得到。10为一新化合物,12和13为一混合物。第四部分薯蓣属植物甾体化合物及生物活性研究进展对自1930年代以来从薯蓣属植物中国内外分离报道的甾体化合物及其生理活性进行了总结,共收集出体化合物149个,其中皂苷元41个,呋甾型皂苷33个,螺甾型皂苷41个,降甾型皂苷或配基15个,胆甾型化合物19个,参考文献85篇,并对薯蓣属植物甾体化合物类型及其生物活性进行了总结和讨论。
其他摘要Steroidal saponins are a kind of important secondary metabolites occurring and distributing in plants, and exhibit a variety of biological activities such antiinflammatory, antibacteria, antifungus, antitumor, antiaging, antifertility, reducing blood sugar, hypotenuse, etc, and have been investigated to ward the development of new natural medicines and to prove the efficacy of traditional herbal medicines. Their aglycones are an important raw material for the synthesis of steroidal hormone drugs, also. The chemical constituents of two medicinal plants and a wild edible plant abounding steroidal saponins: Smilacina atropurpurea (Franch.) Wang et Tang, Dioscorea composita Hemsl and Dioscorea parviflora C.T.Ting, were ingestigated in this thesis. Eight new compounds were isolated by chromatography of slic gel, RP-18, Diaion, etc, and identified on the basis of UV, IR, 2D-NMR, MS, X-ray and chemical methods, together with thirty known compounds. And the inhibitory activity of steroidal saponins from S. atropurpurea on K562 cell was assayed. The thesis consists of four parts: Part A: Constituents from Smilacina atropurpurea and the Inhibitory Activity on K562 cell Zhuyecai [Smilacina atropurpurea (Franch.) Wang et Tang., Liliaceae] is a perennial herb plant. The shoot aerial part of it is a wild edible vegetable at minority Zang, Lisu, Naxi in southwest of Sichuan, northwest of Yunnan and Tibet. Four new steroidal saponins, diosgenin 3-0-α-L-rhamnopyranosyl-(l→3)-[6-0-palmitox-yl]-O-β-D-galactopyranoside(4, smilacinoside A), diosgenin 3-O-α-L- rhamnopyran-osyl-(l→2)-O-β-D-galactopyranoside(5, smilacinoside B), 26-O-β-D-glucopyranosyl -(25R)-furost-5-en-3β, 22α, 26-triol 3-O-α-L-rhamnopyranosyl-(l→2)}-β-D-galact-opyranoside(6, smilacinoside C), 26-O-β-D-glucopyranosyl-22-OCH3-(25R)-furost-5-en-3β , 26-dioi 3-O-α- L-rhamnopyranosyl-(l→2)-β-D-galactopyranoside(7, smilacinoside D), were isolated from MeOH extract of the dry aerial parts of Smilacina atropurpurea, together with ten known compounds, thymidine(l), adenosi- ne(2), 2'-deoxyadenosine(3), diosgenin 3-O-β-D-glucopyranosyl-(l→2)-β-D-glucop-yranosyl-(l→4) -β-D- galactopyranoside (8, funkioside D), diosgenin 3-O-β-D-glucopyranosyl-[β-D-xyloyranosyl-(l→3)]-β-D-glucopyranosyl-(l→4)-β-D-galacto-pyranoside (9, aspidistrin), 26-O-β-D-glucopyranosyl-22-OCH3-(25R)-furost-5-en-3β, 26-diol 3-O-β-D-glucopyranosyl-(l→2)-β-D-glucopyranosyl-(l→4)-β-D-galactopyr-anoside(10), daucosterol(ll), n-triacoatanol(12), palmitic acid(13), neotigogenin 3-O-β-D-glucopyranosyl-[β-D-xylopyranosyl-(l→3)]-β-D-glucopyranosyl-(l→4)-β-D-galactopyranoside(14, diuranthoside A). The structures of them were elucidated on the basis of spectroscopic, X-ray and chemical methods. Among them, 1, 2 and 3 are nucleosides, and 3 was isolated from plant for the first time; and 14 was isolated from the rhizomes of it. The steroidal saponins isolated from Smilacina atropurpurea were tested against K562 cancer cell line, and compounds 5, 8 and 9 were demonstrated to have a significant cytotoxicity with an IC50 value 1.09、 2.93、0.47 μg/ml, respectively. In addition, the chemical constituents of the dry aerial parts of S. atropurpurea were compared with the fresh aerial parts and the fresh rhizomes. And the results showed that the constituents of fresh aerial parts were similar with the dry aerial parts, and different with the fresh rhizomes. The rhizomes of it only yielded a few steroidal saponins. Part B: Constituents frqm Dioscorea composita Hemsl Dioscorea composita Hemsl.(Dioscoreaceae) is a large perennial herb and originated from Mexico. It is a raw material of diosgenin for the synthesis of steroid hormone drugs and cultivated at tropical part of Yunnan. From the MeOH extract of the dried rhizomes of a cultivated of D, composita at Xishuangbanna of Yunnan, China, yielded eleven compounds, and elucidated as l,3-bis-(2-hydroxy-4-methoxyphenyl)-propane(l), l,3-bis-(2,4-dihydroxyphenyl)-propane(2), 1 -(2'-hydroxy-4'-O-P-D-glucopyranosypheny l)-3 -(2 ", 4"-dihydroxy phenyl)propane(3), prosapogenin A of dioscin(4), dioscin(5), asperin(6), methyl protodioscin(7), protodioscin(8), methyl asperoside(9), asperoside(lO), palmitic acid(ll). Among them, 1, 2 and 3 were new diarylpropanes. 6, 9 and 10 were isolated from D.composita for the frist time, 7 and 9 are the conversion of 8 and 10 in MeOH. Part C: Constituents from Dioscorea parviflora C.T.Ting. Dioscorea parviflora, belongs to genus Dioscorea, is an endemic plant and mainly distributed in Yunnnan, China. It is an important raw material of diosgenin for the synthesis of steroid hormone drugs. Thirteen compounds, deacylbrownioside(l), diosgenin-diglucoside(2), prosapogenin A of dioscin(3), dioscin(4), deltonin(5), deltoside(6), methyl deltoside(7), diosgenin 3-O-β-D-glucopyranosyl-(l→3)-β-D-glucopyranosyl-(l→4)-[α-L-rhamnopyranosyl-(l→2)]-β-D-glucopyranoside(8), parvifloside(9), methyl parvifloside(lO), diosgenin(ll), p-sitosterol .& stigmasterol (12&13) were isolated and identified from the EtOH extract of the fresh rhizome of it. Among them, compound 1, 2, 4 and 7 were were obtained from it for the first time, and compound 10 was a new compound; and compounds 12 and 13 were mixed. Part D: Advanced on the steroidal compounds and biological activities from Dioscorea L. The advances on the steroidal compounds and biological activities from the genus Dioscorea spp. were reviewed since 1930. And collected compounds 140, including 41 sapogenins, 41 spirostol glycosides, 33 furostol glycosides, 15 pregnane glycosides and 19 cholestane compounds, ref. 85.
页数137
语种中文
文献类型学位论文
条目标识符http://ir.kib.ac.cn/handle/151853/736
专题昆明植物所硕博研究生毕业学位论文
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杨顺丽. 竹叶菜、菊叶薯蓣和小花盾叶薯蓣的化学成分与抗癌活性研究[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,2004.
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