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题名: 五种药用植物的化学成分和生物活性研究
作者: 李 小 年
学位类别: 博士
答辩日期: 2009-05-27
授予单位: 中国科学院昆明植物研究所
授予地点: 昆明植物研究所
导师: 孙汉董
关键词: 香茶菜属 ; 五味子属 ; 云南红景天 ; 瑞香狼毒 ; 二萜 ; 木脂素 ; 细胞毒活性 ; 抗HIV活性
学位专业: 植物学
中文摘要: 本论文由六章组成,前五章论述了五种药用植物[德钦大叶香茶菜(Isodon grandifolia var. atuntzensis C. Y. Wu)、毛萼香茶菜(Isodon eriocalyx (Dunn) Hara)、铁箍散(Schisandra propinqua var. sinensis Oliv.)、云南红景天(Rhodiola yunnanensis (Franch.) S. H. Fu)和瑞香狼毒(Stellera chamaejasme Linn.)]的化学成分及部分化合物的相关生物活性研究,第六章综述了2001 – 2009年间非香茶菜属植物中的对映-贝壳杉烷型二萜的研究进展。 利用各种色谱技术,波谱分析以及单晶X-衍射等方法从上述五种药用植物中共分离鉴定了146个化合物,其中42个为新化合物。化合物类型涉及二萜(包括对映-贝壳杉烷型及其二聚体、松香烷型、对映-松香烷型、对映-阿替烷型、甘西鼠尾草烷型和白鼠尾草烷型)、三萜、甾体、倍半萜、单萜、生物碱、酰胺、苷类、香豆素、脂肪酸以及木脂素、黄酮等酚性成分。首次从香茶菜属植物中分离得到1个结构新颖的C23骨架(przewalskiiane型)萜类化合物、4个apianane型萜类化合物和1个abietane型二萜生物碱;首次从红景天属植物中分离得到3个结构新颖的大环酰胺类化合物。 对德钦大叶香茶菜中的部分二萜化合物和瑞香狼毒中的双黄酮成分进行了初步的体外细胞毒活性测试,发现对映-贝壳杉烷型二萜有较强的活性,而松香烷型二萜和双黄酮基本无细胞毒活性;另外对铁箍散中的大部分木脂素进行了抗HIV活性测试,它们显示不同程度的活性,活性最好的tiegusanin G (7)治疗指数TI值大于25。 第一章 德钦大叶香茶菜的化学成分和细胞毒活性研究 德钦大叶香茶菜(Isodon grandifolia var. atuntzensis C. Y. Wu)为灌木,极多分枝,高1.2 – 1.8 米,产云南西北部,四川西部;生于山坡草地,海拔2700 - 3400米。从采自云南德钦的该植物地上部分共分离鉴定了30个化合物,包括6个新化合物。除了化合物9, 10, 14和27,其余的均为首次从该种植物中分离得到。其中萜类化合物26个:包括两种稀有C23骨架(przewalskiiane和apianane)的萜类化合物(1, 3 – 6),1个松香烷型二萜生物碱(2),9个松香烷型二萜,4个对映-贝壳杉烷型(涉及3种骨架类型)二萜, 1个香树烷型倍半萜,1个愈创木烷型倍半萜,4个紫罗兰酮类降倍半萜,和一个薄荷烷型单萜。同时,对得到的部分二萜化合物进行了初步的细胞毒活性筛选,对映-贝壳杉烷型二萜化合物对大多数肿瘤细胞株均显示不同程度的抑制作用,而松香烷型二萜基本无活性。 第二章 毛萼香茶菜的化学成分研究 毛萼香茶菜 (Isodon eriocalyx (Dunn) Hara)又名虎尾草、四稜蒿和沙虫药等,为多年生草本或灌木,高约0.5-3米。产云南,四川西部,贵州南部,广西西部;生于山坡阳处,灌丛中,海拔750-2600米。叶治脚气,根止泻止痢。从采自四川泸定的该植物的地上部分共分离鉴定了43个化合物,其中31个为二萜化合物(16个新的):包括23个对映-贝壳杉烷型二萜(涉及C-20位未被氧化型、C-20位被氧化型、6,7-断裂-螺环-内酯型、延命素型、7,20-环氧型及其二聚体等多种结构类型),7个对映-松香烷型二萜和1个阿替烷型二萜。以Maoecrystal M为代表的一些列7,20-环氧型和6,7-断裂-螺环-内酯型对映-贝壳杉烷二萜的发现,说明了不同产地的同种植物间次生代谢产物的共性;而一系列结构新颖的对映-松香烷型二萜、阿替烷型二萜和延命素型对映-贝壳杉烷二萜的发现,又说明同种植物因生境的不同而导致次生代谢产物的差异。 第三章 铁箍散的化学成分和抗HIV活性研究 铁箍散(Schisandra propinqua var. sinensis Oliv.)又名血糊藤、香巴戟和小血藤等,落叶木质藤本,叶坚纸质,产于陕西、甘肃南部、江西、河南、湖北、湖南、四川、贵州、云南中部至南部。生于沟谷、岩石山坡林中。海拔500-2000米。该植物在神农架地区民间用于治疗风湿麻木、跌打损伤、胃痛、脉管炎等疾病。从采自四川二郎山的铁箍散的地上部分共分离鉴定了34个化合物,其中木脂素32个(17个新的),除了化合物34,其余的均为首次从该种植物中分离得到。 木脂素主要为联苯环辛二烯型(18个),另外还有4-芳基四氢萘型、2,3-二甲基-1,4-二芳基丁烷型、单四氢呋喃型、和新异木脂素共5种类型。同时,对分离得到的23个木脂素进行了抗HIV-1活性筛选。结果表明大部分化合物抗HIV-1活性较弱或没有活性,只有少数几个联苯环辛烯木脂素(7、16、14)具有相对较强的活性,尤其是tiegusanin G (7),EC50值为7.9 μg/mL,治疗指数TI值大于25。 第四章 云南红景天的化学成分研究 云南红景天(Rhodiola yunnanensis (Franch.) S. H. Fu)又名三台观音、铁脚莲,多年生草本,根茎粗长,直径可达2厘米,产西藏、云南、贵州、湖北西部、四川。生于海拔2000-4000米的山坡林下。全草药用,有消炎、消肿、接筋骨之效。从采自云南香格里拉的该植物根中共分离得到了20个化合物,其中化合物1 – 3为一类结构新颖的大环酰胺类化合物。除了没食子酸、β-谷甾醇和胡萝卜苷(17, 19, 20),其余的均为首次从该植物中分离得到,其结构类型主要是苷类和酚性成分,这与前人报道的该属其它种的情况基本相似。另外,我们首次从该植物中分离得到了目前公认的有效成分酪醇和有毒成分百脉根苷,而没有发现红景天苷,这与文献报道的结果(云南红景天中红景天苷含量很低)是一致的,同时较大量百脉根苷的存在也说明该种植物不能作为《中国药典》规定的红景天或代用品种。 第五章 瑞香狼毒的化学成分和细胞毒活性研究 瑞香狼毒(Stellera chamaejasme Linn.)又名西北狼毒,民间称为断肠草、山萝卜、红狼毒等,为多年生草本,高20-50厘米,根茎木质,产我国北方各省区及西南地区。生于海拔2600-4200米的干燥而向阳的高山草坡、草坪或河滩台地。俄罗斯西伯利亚也有分布。瑞香狼毒的毒性较大,可以杀虫;根入药,有祛痰、消积、止痛之功效,外敷可治疥癣。从采自云南香格里拉的该植物中共分离鉴定了19个化合物,其中多数化合物(1 – 3, 5 – 9, 11, 14, 16 – 17)为首次从该植物中分离得到,而没有得到具有抗癌活性的瑞香烷型二萜化合物,说明同种植物因生境的不同而导致了次生代谢产物的差异。同时,对得到的4个双黄酮进行了初步的细胞毒活性筛选,结果显示均无活性,这也从另一个角度说明瑞香狼毒的抗癌活性成分主要是瑞香烷型二萜类化合物,因此,该植物作为药用时,瑞香烷型二萜应作为重要的检测指标。 第六章 非香茶菜属植物中的对映-贝壳杉烷型二萜研究进展 总结了2001 – 2009年间从非香茶菜属植物中发现的对映-贝壳杉烷型二萜化合物及其生物活性的研究进展,共综述了137个化合物。
英文摘要: This dissertation is composed of six chapters, in which the chemical and bioactive constituents of five medicinal plants, Isodon grandifolia var. atuntzensis C. Y. Wu, Isodon eriocalyx (Dunn) Hara, Schisandra propinqua var. sinensis Oliv., Rhodiola yunnanensis (Franch.) S. H. Fu, and Stellera chamaejasme Linn., have been phytochemically studied. 146 compounds, including 42 new ones, were isolated from the above mentioned five species. Their structures were established on the basis of extensive spectroscopic methods in conjunction with single-crystal X-ray diffraction analysis. Chapter 6 is a review about the chemical and bioactivities of new kauranoids and ent-kauranoids in the plants apart from the Isodon species between 2001 and 2009. These compounds include diterpenoids (ent-kaurane, ent-kaurane dimer, ent-abietane, ent-atisane, abietane, przewalskiiane and apianane), triterpenoids, sesquiterpenes, monoterpenoids, lignans, flavones, alkaloids, amides, glycosides, coumarins, steroids, and fatty acids. Among these compounds, atuntzensin B (1) belonging to a rare C23 skeleton with a 6/6/7 carbon cycle system, atuntzensin D (3) belonging to a rare C23 skeleton with a 6/6/5/5 carbon cycle system, and one novel abietane type alkaloid, atuntzensin C (2), have been isolated from I. grandifolia var. atuntzensis, which is the first time in Isodon spicies. As well as, three novel amides with a rare large ten-membered ring isolated from R. yunnanensis. Some diterpenoids from I. grandifolia var. atuntzensis and four biflavonoids from S. chamaejasme were evaluated for their cytotoxic activities against several kinds of human tumor cell lines in vitro. ent-Kauranoids of them exhibited strong activity, but abietanoids and biflavonoids had nearly not activities against these cell lines. Furthermore, the majority of lignans from S. propinqua var. sinensis were evaluated for inhibitory activities against HIV-1. Tiegusanin G (7) showed anti-HIV-1 activities with an EC50 value of 7.9 µM and a therapeutic index (TI) of > 25. Chapter 1. Studies on Chemical Constituents and Cytotoxic Activity of Isodon grandifolia var. atuntzensis Isodon grandifolia var. atuntzensis is a perennial herb distributed in the northwest of Yunnan and the west of Sichuan provinces of China. Thirty compounds including twenty-six terpenoids (six new ones) were isolated from the ethyl acetate fraction of the aerial parts of this plant. Atuntzensin B (1) belonging to a rare C23 skeleton with a 6/6/7 carbon cycle system, atuntzensin D (3) belonging to a rare C23 skeleton with a 6/6/5/5 carbon cycle system, and one novel abietane type alkaloid, atuntzensin C (2), were isolated from this plant, which was the first time in Isodon spicies. Some diterpenoids from this plant were evaluated for their cytotoxic activities against several kinds of human tumor cell lines in vitro. ent-Kauranoids of them exhibited strong activities, but abietanoids had nearly not activities against these cell lines. 1. Atuntzensin B (1)* 2. Atuntzensin C (2)* 3. Atuntzensin D (3)* 4. rel-(5S, 6S, 7S, 10R, 12R, 13S)-7-Hydroxyapiana-8,14-diene-11,16-dion-(22,6)- olide (4) 5. rel-(5S, 6S, 7S, 10R, 12S, 13R)-7-Hydroxyapiana-8,14-diene-11,16-dion-(22,6)- olide (5) 6. rel-(5S, 6S, 7R, 10R, 12S, 13R)-7-hydroxyapiana-8,14-diene-11,16-dion-(22,6)- olide (6) 7. Atuntzensin E (7)* 8. Isorosmanol (8) 9. Carnosol (9) 10. Rosmanol (10) 11. Epirosmanol (11) 12. 7β-Methoxyrosmanol (12) 13. Rosmaquinone (13) 14. Atuntzensin A (14) 15. Atuntzensin F (15)* 16. Lushanrubescensin C (16) 17. Enmenin monoacetate (17) 18. Enmenin (18) 19. Trichorabdal A (19) 20. Isodonsesquitin B (20)* 21. 10-Epiteuclatriol (21) 22. (3R,6R,7E)-3-Hydroxy-4,7-megastigmadien-9-one (22) 23. (+)-(3S)-3-Hydroxy-β-ionone (23) 24. 3-Hydroxy-β-damascone (24) 25. (6R)-3-Oxo-α-ionol (25) 26. 1,2-Dihydroxylimonene (26) 27. 5-Hydroxy-7,4´-dimethoxyflavone (27) 28. 3-Formylindole (28) 29. Coniferadehyde (29) 30. 4-Hydroxybenzaldehyde (30) Note * new compound. Chapter 2. Studies on Chemical Constituents of Isodon eriocalyx Isodon eriocalyx, a perennial herb, is mainly distributed in Yunnan, the south of Guizhou, and the west of Sichuan provinces and Guangxi autonomous region. Its leaves and stems have respectively been used for treating beriberi and treatment of diarrhea and dysentery. Sixteen new diterpenoids, along with fiveteen known ones and twelve other compounds, were isolated and identified from the aerial parts of this plant collected in Luding County, Sichuan province. The classes of these diterpenoids include ent-kaurane type (C-20-non-oxygenated type, C-20-oxygenated type, 6,7-seco-spiro-lactone type, enmein type, 7,20-epoxy type, and its dimer), ent-abietane type, and ent-atisane type. Among these compounds, maoecrystal M, and many 7,20-epoxy type and 6,7-seco-spiro-lactone type of ent-kauranoids have been reported in many previous papers, in which the species were collected in Yunnan and Guizhou provinces. However, all enmein type of ent-kauranoids, ent-abietanoids, and ent-atisanoids were not mentioned in those literatures. The results showed that the constituents were different from those isolated from the same species collected in different erea and confirmed that the habitat of the plant greatly affected its secondary metabolites. 1. Maoesin A (1)* 2. ent-Kaurane-3β,16β-diol (2) 3. Maoesin B (3)* 4. Maoesin C (4)* 5. Maoesin D (5)* 6. Maoesin E (6)* 7. Maoecrystal M (7) 8. Xerophilusin H (8) 9. Maoecrystal J (9) 10. Longikaurin C (10) 11. Effusanin B (11) 12. Maoecrystal R (12) 13. Kamebacetal A (13) 14. Henryin (14) 15. Maoesin F (15)* 16. Maoesin G (16)* 17. Nodosin (17) 18. Enmin (18) 19. Maoesin H (19)* 20. 3-Acetyl trichorabdal C (20) 21. Coetsin B (21) 22. Rabdosichuanin A (22) 23. Sculponeatin C (23) 24. Maoesin I (24)* 25. Maoesin J (25)* 26. Maoesin K (26)* 27. Maoesin L (27)* 28. Maoesin M (28)* 29. Maoesin N (29)* 30. Maoesin O (30)* 31. Maoesin P (31)* 32. (+)-1-Hydroxypinoresinol (32) 33. (+)-Lariciresinol (33) 34. Quercetin (34) 35. Isothymusin (35) 36. Acacetin (36) 37. Apigenin (37) 38. 2,2′-Dihydroxyacetophenone (38) 39. Oleanolic acid (39) 40. Loliolide (40) 41. Octanoic acid (41) 42. Palmitic acid (42) 43. Stearic acid(43) Note * new compound Chapter 3. Studies on Chemical Constituents and Anti-HIV Activity of Schisandra propinqua var. sinensis Schisandra propinqua var. sinensis belongs to the genus Schisandra of the family Schisandraceae. It is a climbing plant widely distributed in China. This plant, popularly known as “tie-gu-san” in Shenlongjia district of Hubei Province, is used in folk medicine for the treatment of arthritis, traumatic injury, gastralgia, angeitis and related diseases. Thirty-four compounds, including thirty-two lignans (seventeen new ones) were isolated from the stems and leaves of this plant collected in Erlang Mountain Area of Sichuan Province. All of the lignans were isolated from this plant for the first time, of which eighteen ones belongs to dibenzocyclooctadiene lignans. Furthermore, the majority of lignans were evaluated for inhibitory activities against HIV-1. Tiegusanin G (7) showed anti-HIV-1 activities with an EC50 value of 7.9 µM and a therapeutic index (TI) of > 25. 1. Tiegusanin A (1)* 2. Tiegusanin B (2)* 3. Tiegusanin C (3)* 4. Tiegusanin D (4)* 5. Tiegusanin E (5)* 6. Tiegusanin F (6)* 7. Tiegusanin G (7)* 8. Tiegusanin H (8)* 9. Tiegusanin I (9)* 10. Tiegusanin J (10)* 11. Tiegusanin K (11)* 12. Tiegusanin L (12)* 13. Tiegusanin M (13)* 14. Methyl schisantherin F (14) 15. Kadsurin (15) 16. Interiotherin C (16) 17. (7S,8S,R-biar)-6,6,7,8-tetrahydro-12,13-methylenedioxy-1,2,3,14-tetramethoxy- 7,8- dimethyldibenzo[a,c]cycloocten-9-one (17) 18. Methylisogomisin O (18) 19. Tiegusanin N (19)* 20. Tiegusanin O (20)* 21. Tiegusanin P (21)* 22. Tiegusanin Q (22)* 23. Longipedunrin D (23) 24. meso-Dihydroguaiaretic acid (24) 25. meso-Monomethyl dihydroguaiaretic acid (25) 26. 4,4′-((2R,3S)-2,3-Dimethylbutane-1,4-diyl)bis(1,2- dimethoxybenzene) (26) 27. Galgravin (27) 28. Dimethyl-tetrahydrofuroguaiacin (28) 29. Austrobailignan-7 (29) 30. (-)-Machilusin (30) 31. (2R,3S,4R,5R)-2-(3,4-Dimethoxyphenyl)-3,4-dimethyl-5-piperonyltetrahydrofuran (31) 32. Marphenol H (32) 33. Cirsimaritin (33) 34. Stearic acid (34) Note * new compound Chapter 4. Studies on Chemical Constituents of Rhodiola yunnanensi Rhodiola yunnanensis is a perennial herb distributed in Tibet Autonomous Region, Yunnan, Guizhou, Sichuan provinces and the west of Hubei Province. The whole plant has been used in folk medicine for eliminating inflammation and detumescence. Twenty compounds, including three novel amides with a rare large ten-membered ring, isolated from rhizomes of this plant collected in Shangrila County, Yunnan province. Except for gallic acid, β-sitisterol, and dancosterol (17, 19, 20), other seventeen compounds were isolated from this species for the first time. The majority of ones were glycosides and phenol constituents, which have been isolated from other Rhodiola species. It is noteworthy that both of effective constituent tyrosol (16), and toxiferous component rhodiocyanoside A (15) acknowledged recently were obtained from this plant, which were the important criterion if this spicies could been used as a Traditional Chinese Medicine defined Chinese Pharmacopeia. 1. Rhodiolamide A (1)* 2. Rhodiolamide B (2)* 3. Rhodiolamide C (3)* 4. Isolariciresinol (4) 5. Cyclo-olivil (5) 6. Pollenitin (6) 7. Gossypetin 7-O-β-D-glucopyranosyl(1-3)-α-L-rhamnopyranoside (7) 8. Kaempferol 7-O-α-L- rhamnopyranoside (8) 9. Crenuloside (9) 10. Kenposide A (10) 11. Rhodioloside E (11) 12. Octyl α-L-arabinopyranosyl(1-3)-β-D-glucopyranoside (12) 13. n-Octyl-β-D-glucopyranoside (13) 14. Crenulatin (14) 15. Rhodiocyanoside A (15) 16. Tyrosol (16) 17. Gallic acid (17) 18. 4-Hydroxybenzoic acid (18) 19. β-Sitisterol (19) 20. Dancosterol (20) Note * new compound. Chapter 5. Studies on Chemical Constituents and Cytotoxic Activity of Stellera chamaejasme Stellera chamaejasme, a perennial herb, is mainly distributed in the north provinces and southwest area of China, and Siberian of Russia. Its rhizome is a kind of Traditional Chinese Medicine, and has being used to expell phlegm, remove food retention, and relieve pain. Nineteen known compounds were isolated and identified from this plant collected in Shangrila County, Yunnan province, but no daphnanoids with strong cytotoxic activities, such as gnidimacrin, were obtained. The majority of them were obtained from this plant for the first time, but all they have been isolated from other species of family Thymelaeaceae. Four biflavonoids from it were evaluated for their cytotoxic activities against several kinds of human tumor cell lines in vitro, but they had nearly not showed any activities against these cell lines. This result conformed once again that daphnanoids were mainly active constituents, which should been measured as important objects when this plant is used as a Traditional Chinese Medicine. 1. (–)-Dihydrosesamin (1) 2. Pluviatolide (2) 3. Bursehernin (3) 4. Umbelliferone (4) 5. Loliolide (5) 6. 4-Hydroxy-3,5-dimethoxybenzaldehyde (6) 7. p-Cresol (7) 8. Wikstrol B (8) 9. Daphnodorin G (9) 10. Chamaechromone (10) 11. Genkwanol A (11) 12. 1,5-Diphenyl-1-pentanone (12) 13. Syringin (13) 14. 2,6-Dimethyl-2-octylene (14) 15. Tridecanoic acid (15) 16. Glycerol 2-octadecanoate (16) 17. 1-Monolinolenin-O- glucoside (17) 18. β-Sitisterol (18) 19. Dancosterol (19) Note * new compound Chapter 6. Ent-kauranoids in the plants apart from the Isodon species New ent-kauranoids and their bioactivities in the plants apart from the Isodon species reported from 2001 to 2009 were summarized. 137 compounds were presented.
语种: 中文
内容类型: 学位论文
URI标识: http://ir.kib.ac.cn/handle/151853/408
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五种药用植物的化学成分和生物活性研究.李 小 年[d].中国科学院昆明植物研究所,2009.20-25
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