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题名: 蓝桉、清香木及三种香茶菜属植物化学成分的分离、结构及生物活性
作者: 侯爱君
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: 孙汉董
关键词: 植物化学 ; 蓝桉 ; 清香木 ; 香茶菜属 ; 化学成分
学位专业: 植物学
中文摘要: 本论文分七章,第一章对蓝桉(Eucalyptus globulus Labill.)中可水解丹宁及多元酚类化合物的分离与鉴定进行了详细论述。第二章阐明了清香木(Pistacia weinmannifolia J.Poisson ex Franch)中可水解丹宁及多元酚类化合物的结构以及叶中的挥发性成分。第三、四和五章主要论述了三种香茶菜属药用植物—旱生香茶[Isodon xerophilus (C.Y.Wu et H.W.Li) H.Hara],叶穗香茶菜[Isodon phyllostachys (Diels) Hara]和疏花毛萼香茶菜[Isodon eriocalyx (Dunn) Hara var.laxifiora C.Y.Wu et H.W.Li]中新二萜的结构。第六章是生物活性研究,分别论述了蓝桉中部分化合物的抗菌活性,清香木中部分化合物的抗肿瘤活性及旱生香茶菜中部分二萜的抗肿瘤活性。第七章对丹宁的化学及生物活性进行了综述。从上述五种药用植物中共鉴定化合物88个(其中挥发性成分25个),其中3个丹宁和13个二萜为新化合物。丹宁(tannins)是植物体内产生的一类具有复杂结构的多元酚类化合物。由于其极性强、稳定性差,在分离过程中易受酸、碱、酶、热等因素的影响而发生氧化、聚合、分解等反应,因此过去对中草药中其它类成分(如:生物碱、黄酮、香豆素、萜类、皂甙、木脂素等)研究得比较深入,对丹宁类化合物却认识甚少。1975年以后,日本奥田拓男(T. Okuda)、西冈武夫(I. Nishioka)教授等开始对药用植物中的丹宁类成分进行研究,取得了突破性进展,已从不同药用植物中得到了数百种不同结构类型的丹宁,包括四聚体在内的可水解丹宁聚合体就有100多个,大大丰富了丹宁化学的内容。同时,还发现一些丹宁具有显著的抗肿瘤、抗氧化、抑制酶活性和抗病毒等作用。这些活性的发现,引起了各国学者的广泛兴趣。含丹宁的中草药资源十分丰富,虽然近十年来我国对中草药丹宁成分的研究取得了较大进展,但仍有大量的含丹宁中草药的成分与活性需要阐明。我们所选择的两种药用植物一蓝桉和清香木,含有丰富的丹宁及多元酚类化合物,在云南省的资源极为丰富,而且通过活性初筛发现蓝桉叶和清香木叶水溶性成分的粗提物分别具有一定的抗菌和抗肿瘤活性。为了寻找其活性成分,阐明其中丹宁及多元酚类化合物的结构,我们对这两种药用植物的化学成分进行了研究。从蓝桉叶中分离鉴定了7个可水解丹宁及相关的多元酚类化合物,它们分别是:eucaglobulin (1),tellimagrandin I (2),eucalbanin C (3),2-O-digalloyl-1,3,4-tri-O-galloyl-β- D-glucose (4),6-O-digalloyl-1,2,3-tri-O-galloyl-β-D-glucose (5),gallic acid (6)和(+)-catechin (7)(Figure 1)。其中蓝桉素(eucaglobulin,1)为一新奇的没食子丹宁与单萜的结合体,eucalbanin C (3)为可水解丹宁二聚体。从清香木叶中分离鉴定了18个丹宁及其它多元酚类化合物,它们分别是:pistafolin A (1),pistafolin B (2),octa-O-galloyl-β-D-glucose (3) 3-O-galloylshikimic acid (4),5-O-galloylshikimic acid (5), 3,4-di-O-galloylquinic acid(6),myricetin-3-O-α-L- rhamnopyranoside (7),quercetin-3-O-α-L-rhamnopyranoside (8),myricetin-3-O-(3"-O-galloyl)-α-L-rhamnopyranoside (9),myricetin-3-O-(6"-O-galloyl)-β-D-galactopyranoside (10), myricetin-3-O-(6"-O-galloyl)-β-D-glucopyranoside (11),myricetin-3-O-β-D-glucuronide (12),quercetin-3-O-β-D-glucuronide (13),1-O-β-D-(6'-O-galloyl)- glucopyranosyl-3-methoxy-5-hydroxybenzene (14),gallic acid (15),methyl gallme (16),(+)-catechin (17)和(+)-gallocatechin (18)(Figure 2)。其中清香木甲素和乙素(pistafolins A-B,1-2)为2个新的没食子丹宁,其余化合物(3-18)均为首次从该植物中分离得到。此外,利用GC/MS,鉴定了叶精油中的25个成分。唇形科(Labiatae)香茶菜属(Isodon)植物,经多年的化学和生物活性研究结果表明,该属植物富含对映-贝壳杉烷型二萜化合物,且大都具有抗菌、消炎和抗肿瘤活性。通过抗肿瘤活性筛选发现,旱生香茶菜叶的丙酮提取物和其乙酸乙酯部分对3种肿瘤细胞株 (K562,HL-60和MKN-28)的增殖有较强抑制作用,乙酸乙酯部分对人结肠癌细胞株(HCT)的生长有抑制倾向。为寻找活性成分,我们对乙酸乙酯部分进行了深入研究,分离鉴定了19个化合物,分别是:xerophilusin A (1),xerophilusin B (2),xerophilusin C (3),xerophilusin D (4),xerophilusin E (5),xerophilusin F (6),xerophilusin G (7),xerophilusin H (8),xerophilusin I (9),xerophilusin J (10),xerophilusin K (11),macrocalin B (12),rosthorin A (13),phyllostachysin A (14),longikaurin B (15),rabdotemin D (16),oleanolic acid (17),6,7,4'-trihydroxy-5-methoxyflavone (18)和caffeic acid (19)。从正丁醇部分分离鉴定了4个酚性化合物,分别是:rosmarinic acid (20),mtin (21),quercitrin (22)和quercetin (23)(Figure 3)。其中,旱生香茶菜素A-K (xerophilusins A-K,1-11)为11个新的对映-贝壳杉烷型二萜化合物,其余化合物(12-23)均为首次从该植物中得到。11个新二萜的结构类型较为丰富,包括了7,20:14,20-二环氧化,7,20:19,20-二环氧化,7,20:3,20-二环氧化,7,20-环化和7,20-环氧化-对映-贝壳杉烷型二萜化合物。旱生香茶菜素E(5)为以7,20:3,20-二环氧化-对映-贝壳杉-16-烯-15-酮作为基本骨架的新奇类型化合物。此外,从叶穗香茶菜中分离鉴定了6个化合物,分别是:phyllostachysin C (1)sculponeatins B (2),sculponeatins C (3),nodosin (4),ursolic acid (5) 和2α-hydroxyursolic acid (6) (Figure 4)。其中,叶穗香茶菜丙素(phyllostachysin C,1)为一新二萜化合物。从疏花毛萼香茶菜中分离鉴定了9个化合物,分别是:laxiflorin D (1),laxiflorin A (2),maoecrystal A (3),maoecrystal B (4),maoecrystal C (5),maoecrystal P (6),eriocalyxin B (7),cirsimaritin (8) 和2α-hydroxyursolic acid (9) (Figure 5)。其中,疏花毛萼香茶菜丁素(laxiflorin D,1)为一新二萜化合物。在分离、鉴定工作完成后,我们将蓝桉中的部分化合物进行了抗菌活性筛选,两个主成分tellimagrandin I (2) 和eucalbanin C (3) (Figure 1) 对几种供试菌有抑制作用;选择清香木中的部分化合物进行抗肿瘤活性筛选,结果表明gallic acid (15) 和(+)-gallocatechin (18) (Figure 2) 对K562细胞株的增殖有显著抑制作用;将旱生香茶菜中一系列二萜化合物进行抗肿瘤活性研究,结果表明其大都对K562、HL-60、HCT及MKN-28四种细胞株具有显著的细胞毒活性。其中长管香茶菜乙素(longikaurin B,15)、旱生香茶菜素D (xerophilusin D,4) 和K (xerophilusin K,11) (Figure 3) 在受试浓度范围内对4种细胞株生长的IC_(50)值均小于16μg/mL,表明这4个化合物具有较广的抑瘤谱和较强的活性。最后,对丹宁类化合物的化学和生物活性进行了综述。
英文摘要: This thesis consists of seven chapters. The first chapter shows the isolation and identification of hydrolyzable tannins and polyphenols from Eucalyptus globulus Labill. The second chapter presents the structures of hydrolyzable tannins and polyphenols from Pistacia weinmannifolia J. Poisson ex Franch and the constituents of the essential oil. Chapters III-V clarify the structures of new ent-kaurane diterpenoids from three Isodon species [I. xerophilus (C. Y. Wu et H. W. Li) H. Hara, I. phyllostachys (Diels) Hara and I. eriocalyx (Dunn) Hara var. laxifiora C. Y. Wu et H. W. Li]. Chapter VI reports the antibacterial effect of some compounds from E. globulus, the antitumor action of some isolates from P. weinmannifolia and the antitumor activity of most ent-kauranoids from I. xerophilus. Finally, chemistry and biological activity of tannins are reviewed. Besides 25 compounds in the essential oil, 63 compounds from five medicinal plants above were identified, including three new tannins and 13 new ent-kauranoids. Although tannins, a larger group of polyphenolic compounds widely distributed in plants, are often encountered in our lives, little has been known about the significance of their presence until recent years. Modem results of studies indicate that tannin is a new family of bio-active natural organic compounds. Advanced isolating methods and various spectroscopic techniques disclose the structure and classification of tannins. Simultaneously, a series of remarkable biological activities of tannins, such as anti-oxidative activity, host-mediated antitumor action, inhibition of enzyme activity and antiviral effect are also made public. Since 1989, studies on tannins and related polyphenols from medicinal plants have been carried out in China, and encouraging progress have been made. The two medicinal plants, E. globulus and P. weinmannifolia, are rich in tannins and ployphenols and widely distributed in Yunnan province. The extracts of water-soluble constituents from the leaves of these two plants showed potent antibacterial and antitumor activities, respectively. The results led to the isolation and characterization of a series of tannins and polyphenols. From the leaves of E. globulus, eucaglobulin (1), a new complex of gallotannin and monoterpene, was isolated. Its structure was elucidated on the basis of spectral data. Six known hydrolyzable tannins and related polyphenols were also isolated. The structures of these seven compounds are illustrated in Figure 1. 1. Eucaglobulin (1) (new) 2. Tellimagrandin I (2) 3. Eucalbanin C (3) 4. 2-O-digalloyl-1, 3, 4-tri-O-galloyl-β-D-glucose (4) 5. 6-O-digalloyl-1, 2, 3-tri-O-galloyl-β-D-glucose (5) 6. Gallic acid (6) 7. (+)-Catechin (7) From the leaf extract of P. weinmannifolia, two new gallotannins, pistafolins A (1) and B (2), were isolated Their structures were determined by spectral methods. Four known gallotannins (3-6), seven known flavonoid glycosides (7-13), along with five other polypenols (14-18), were also isolated. Besides these constituents, twenty-five compounds in the essential oil of the leaves were also identified by the method of GC/MS. The structures of eighteen compounds are summarized in Figure 2. 1. Pistafolin A (1) (new) 2. Pistafolin B (2) (new) 3. Octa-O-galloyl-β-D-glucose (3) 4. 3-O-galloylshikimic acid (4) 5. 5-O-galloylshikimic acid (5) 6. 3, 4-di-O-galloylquinic acid (6) 7. Myricetin-3-O-α-L-rhamnopyranoside (7) 8. Quercetin-3-O-α-L-rhamnopyranoside (8) 9. Myricetin-3-O-(3"-O-galloyl)-α-L-rhamnopyranoside (9) 10. Myricetin-3-O-(6"-O-galloyl)-β-D-galactopyranoside (10) 11. Myricetin-3-O-(6"-O-galloyl)-β-D-glucopyranoside (11) 12. Myricetin-3-O-β-D-glucuronide (12) 13. Quercetin-3-O-β-D-glucuronide (13) 14. 1-O-β-D-(6'-O-galloyl)-glucopyranosyl-3-methoxy-5-hydroxybenzene (14) 15. Gallic acid (15) 16. Methyl gallate (16) 17. (+)-Catechin (17) 18. (+)-Gallocatechin (18) Results of chemistry and biological activity indicate that plants belonging to the Isodon genus are rich in ent-kaurane diterpenoids, which have been revealed to possess various biological activities such as antitumor, antibacterial and antiinflammatory effects. In our continuing studies on bioactive diterpenoids from this genus, the acetone extract of I. xerophilus has been found to demonstrate significant inhibitory effect on several kinds of human tumor cells. From the most active EtOAc part, eleven new ent-kaurane diterpenoids (xerophilusins A-K, 1-11) were identified, and five known diterpenoids (12-16), together with oleanolic acid (17), 6, 7, 4'-trihydroxy-5-methoxyflavone (18) and caffeic acid (19) were also isolated. From the n-BuOH layer, four phenolic compounds (20-23) were obtained. The structures of twenty-three compounds are listed in Figure 3. 1. Xerophilusin A (1) (new) 2. Xerophilusin B (2) (new) 3. Xerophilusin C (3) (new) 4. Xerophilusin D (4) (new) 5. Xerophilusin E (5) (new) 6. Xerophilusin F (6) (new) 7. Xerophilusin G (7) (new) 8. Xerophilusin H (8) (new) 9. Xerophilusin I (9) (new) 10. Xerophilusin J (10) (new) 11. Xerophilusin K (11) (new) 12. Macrocalin B (12) 13. Rosthorin A (13) 14. Phyllostachysin A (14) 15. Longikaurin B (15) 16. Rabdoternin D (16) 17. Oleanolic acid (17) 18. 6, 7, 4'-trihydroxy-5-methoxyflavone (18) 19. Caffeic acid (19) 20. Rosmarinic acid (20) 21. Rutin (21) 22. Quercitrin (22) 23. Quercetin (23) Moreover, the chemical constituents of other two medicinal plants belonging to the Isodon genus were also investigated. A new ent-kaurane diterpenoid, phyllostachysin C (1), together with five known compounds (2-6), was isolated from the leaves of I. phyllostachys. The structure of 1 was elucidated on the basis of its spectral properties. Six compounds are outlined in Figure 4. 1. Phyllostachysin C (1) (new) 2. Sculponeatin B (2) 3. Sculponeatin C (3) 4. Nodosin (4) 5. Ursolic acid (5) 6. 2α-hydroxyursolic acid (6) A new diterpenoid named laxifiorin D (1) was isolated from the leaves of I. eriocalyx var. laxiflora, whose structure was determined by the spectroscopic methods. Six known ent-kauranoids (2-7), together with cirsimaritin (8) and 2α-hydroxyursolic acid (9) were also isolated. The structures of nine compounds are shown in Figure 5. 1. Laxifiorin D (1) (new) 2. Laxifiorin A (2) 3. Maoecrystal A (3) 4. Maoecrystal B (4) 5. Maoecrystal C (5) 6. Maoecrystal P (6) 7. Eriocalyxin B (7) 8. Cirsimaritin (8) 9. 2α-hydroxyursolic acid (9) After isolation and identification, the biological activity assays were carried out. The antibacterial effects of some compounds from E. globulus were examined. Two main constituents, tellimagrandin I (2) and eucalbanin C (3) (Figure 1), exhibited inhibitory effects on Escherichia coli, Staph. aureus and Staph. epidermidis. The cytotoxie activities against K562 cells of some isolates from P. weinmannifolia were evaluated. Two small molecular phenolic compounds, gallic acid (15) and (+)-gallocatechin (18) (Figure 2) showed significant inhibitory effects on K562 cells. Some compounds from I. xerophilus were tested for their ability to inhibit K562, HL-60, HCT and MKN-28 cells. Most of diterpenoids exhibited significant cytotoxicities against four kinds of human tumor cells above in vitro. The IC_(50) values of xerophilusins D (4), K (11) and longikaurin B (15) against K562, HL-60, HCT and MKN-28 cells are all less than 16 μg/mL, indicating that they have broad spectra inhibiting human tumor cells and strong activity. Finally, a review titled chemistry and biological activity of tannins is presented.
语种: 中文
内容类型: 学位论文
URI标识: http://ir.kib.ac.cn/handle/151853/498
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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