黄药大头茶的化学成分及生物活性研究
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摘要
黄药大头茶(Polyspora chrysandra Cowan.)为茶科(Theaceae)大头茶属(Polyspora)植物,在热带和温带地区均有分布,在我国主要分布于西南部至东南部以及台湾地区,关于其药理活性的研究未见报道,但对其同科的植物进行广泛的研究,发现其在抗肿瘤、抗艾滋病、抗细菌、抗真菌方面均有一定的活性。
为对大头属植物进行系统的化学成分和生物活性研究,以期更好地利用该属的药用植物资源,我们对黄药大头茶根的化学成分和生物活性展开研究。黄药大头茶的根经95%乙醇和50%乙醇回流提取。其95%提取物用水混悬后,分别用石油醚、氯仿、乙酸乙酯和正丁醇萃取,得到4个萃取部分和水层并进行了药理活性筛选。药理筛选结果表明:黄药大头茶的95%和50%醇提物均有一定的保肝作用,其中,95%醇提物的水层部分保肝作用与阳性对照药双环醇相近;除95%醇提物的氯仿部分外,95%的乙酸乙酯,正丁醇,水部分和50%提取物部分均对HIV整合酶均有较好的抑制作用;正丁醇部位进行了柱层析,其组分C、D、E、F部分对多种肿瘤细胞均有较好的抑制作用。
本文对黄药大头茶的95%乙醇提取物的乙酸乙酯和正丁醇部分进行了系统的化学成分研究,从中分离得到了18个化合物,并通过1D、2DNMR,IR,UV,MS及化学方法鉴定了14个化合物的结构。其中包括4个二氢黄酮醇苷类成分:(2R,3R)-3,5,7,4′-四羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(1)、(2R,3S)-3,5,7,4′-四羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(2)、(2S,3S)-3,5,7,4′-四羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(3)和(2S,3S)-3,5,7,3′,5′-五羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(4);4个皂苷类成分:3β-O-β-D-半乳糖(1→2)-[β-D-木糖(1→2)-α-L-阿拉伯糖(1→3)]-β-D-葡萄糖醛酸-16α,28-二羟基-15α-乙酰氧基-22α-当归酰氧基齐墩果-12-烯(5)、3β-O-β-D-半乳糖(1→2)[-β-D-木糖(1→2)-α-L-阿拉伯糖(1→3)]-β-D-葡萄糖醛酸16α,28-二羟基-21β-乙酰氧基-22α-当归酰氧基齐墩果-12-烯(6)、3β-O-β-D-半乳糖(1→2)[-β-D-木糖(1→2)-α-L-阿拉伯糖(1→3)]-β-D-葡萄糖醛酸-16α,28-二羟基-22α-当归酰氧基齐墩果-12-烯(7)和3β-O-α-L-鼠李糖(1→2)-α-L-阿拉伯糖(1→3)-β-D-葡萄糖醛酸-16α-羟基-28-葡萄糖酯齐墩果-12-烯(8);3个木脂素:3-O-glucopyranosyl-epi-lyoniresinol(9)、(-)lyoniresinol 3-O-β-D-glucopyranoside(10)和(+)lyoniresinol 3-O-β-D-glucopyranoside(11);其它类:leonuriside A(12),fraxin(13),胡萝卜苷(14)。其中,化合物1-8为新化合物,9-11为首次从该植物中分离得到。药理筛选结果表明:化合物1-3有较好的保肝活性,5-6有较好的抗肿瘤活性。
Polyspora chrysandra Cowan.belongs to the family Theaceae,which consists of approximately 520 species categorized under 25 different genera.Although the chemistry and bioactivity of the genus Polyspora has seldom been previously reported, the other species of the family Theaceae have been extensively demonstrated.Theaceae species are widely distributed in tropical and warm temperate areas of the world. Bioactive studies on some members of Theaceae family have shown a wide range of activity,including antitumor,anti-HIV,antibacterial and antifungal.In addition,various plants of this family are used as remedies for rheumatism,swelling,traumatic bleeding, tropical ulcers and sores.
A series of pharmacological experiments and systematic analyses of chemical constitutions in the roots of Polyspora chrysandra Cowan have been conducted in this thesis,which placed a foundation for the further exploiture of Polyspora.The dried roots of Polyspora chrysandra Cowan were refluxed by 95%ethanol and concentrated under reduced pressure,then the residue was extracted with petrol ether,CHCl_3,EtOAc and n-BuOH in sequence.The CHCl_3,EtOAc and water portions showed significant inhibitory effect on GalN-induced liver lesion;The CHCl_3,n-BuOH and water portions showed inhibitory effect on HIV integrase.Based on these results,we studied each extract portion and tried to find some chemical compounds related to above bioactivities.
In this thesis,eighteen compounds were isolated from the EtOAc and n-BuOH portions of the 95%ethanolic extract.And their structures were elucidated by spectroscopic methods including IR,MS,HR-MS,1D and 2D-NMR and chemical experiments.These compounds were determined as:(2R,3R)-3,5,7,4'-tetrahydroxy flavanonol-3-O-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamno pyranoside(1),(2R,3S)-3,5,7,4'-tetrahydroxyflavanonol-3-O-α-L-rhamnopyranosyl (1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamnopyranoside(2),(2S,3S)-3,5,7,4'-tetra hydroxyflavanonol-3-O-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamnopyranoside (3),(2S,3S)-3,5,7,3',5'-penthydroxy flavanonol-3-O-α-L-rham nopyranosyl(1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamnopyranoside(4),16α,28-diol-15α-acetyloxy-22α-angeloyloxy theasapogenol B 3β-O-β-D-galactopyranosyl(1→2)[-β-D-xylopyranosyl(1→2)-α-L-arabinopyranosyl(1→3)]-β-D-glucopyranosid uronic acid(5),16α,28-diol-21β-acetyloxy-22α-angeloyloxy theasapogenol B 3β-O-β-D-galactopyranosyl (1→2)[-β-D-xylopyranosyl(1→2)-α-L-arabinopyranosyl(1→3)]-β-D-glucopyranosiduronic acid(6),16α,28-diol-22α-angeloyloxy theasapogenol B 3β-O-β-D -galactopyranosyl(1→2)[-β-D-xylopyranosyl(1→2)-α-L-arabinopyranosyl(1→3)]-β-D -glucopyranosiduronic acid(7),16α-hydroxy-28-O-glucopyranosyl-theasapogenol B 3-O-α-L-rhamnopyranoside(1→2)-α-L-arabinopyranosyl(1→3)-β-D-glucopyranosiduronic acid(8),3-O-glucopyranosyl-epi-lyoniresinol(9),(-)-lyoniresinol 3-O-β-D-glucopyranoside(10),(+)-lyoniresinol 3-O-β-D-glucopy ranoside(11), leonuriside A(12),fraxin(13) and daucosterin(14).Among them,compounds 1-8 are new compounds,9-11 were isolated from this genus for the frist time.Compounds 1-3 showed remarkable hepatoprotective activity,5-7 showed potent antitumor activity.
为对大头属植物进行系统的化学成分和生物活性研究,以期更好地利用该属的药用植物资源,我们对黄药大头茶根的化学成分和生物活性展开研究。黄药大头茶的根经95%乙醇和50%乙醇回流提取。其95%提取物用水混悬后,分别用石油醚、氯仿、乙酸乙酯和正丁醇萃取,得到4个萃取部分和水层并进行了药理活性筛选。药理筛选结果表明:黄药大头茶的95%和50%醇提物均有一定的保肝作用,其中,95%醇提物的水层部分保肝作用与阳性对照药双环醇相近;除95%醇提物的氯仿部分外,95%的乙酸乙酯,正丁醇,水部分和50%提取物部分均对HIV整合酶均有较好的抑制作用;正丁醇部位进行了柱层析,其组分C、D、E、F部分对多种肿瘤细胞均有较好的抑制作用。
本文对黄药大头茶的95%乙醇提取物的乙酸乙酯和正丁醇部分进行了系统的化学成分研究,从中分离得到了18个化合物,并通过1D、2DNMR,IR,UV,MS及化学方法鉴定了14个化合物的结构。其中包括4个二氢黄酮醇苷类成分:(2R,3R)-3,5,7,4′-四羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(1)、(2R,3S)-3,5,7,4′-四羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(2)、(2S,3S)-3,5,7,4′-四羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(3)和(2S,3S)-3,5,7,3′,5′-五羟基二氢黄酮醇-3-O-α-L-鼠李糖(1→2)-β-D-葡萄糖(1→2)-α-L-鼠李糖苷(4);4个皂苷类成分:3β-O-β-D-半乳糖(1→2)-[β-D-木糖(1→2)-α-L-阿拉伯糖(1→3)]-β-D-葡萄糖醛酸-16α,28-二羟基-15α-乙酰氧基-22α-当归酰氧基齐墩果-12-烯(5)、3β-O-β-D-半乳糖(1→2)[-β-D-木糖(1→2)-α-L-阿拉伯糖(1→3)]-β-D-葡萄糖醛酸16α,28-二羟基-21β-乙酰氧基-22α-当归酰氧基齐墩果-12-烯(6)、3β-O-β-D-半乳糖(1→2)[-β-D-木糖(1→2)-α-L-阿拉伯糖(1→3)]-β-D-葡萄糖醛酸-16α,28-二羟基-22α-当归酰氧基齐墩果-12-烯(7)和3β-O-α-L-鼠李糖(1→2)-α-L-阿拉伯糖(1→3)-β-D-葡萄糖醛酸-16α-羟基-28-葡萄糖酯齐墩果-12-烯(8);3个木脂素:3-O-glucopyranosyl-epi-lyoniresinol(9)、(-)lyoniresinol 3-O-β-D-glucopyranoside(10)和(+)lyoniresinol 3-O-β-D-glucopyranoside(11);其它类:leonuriside A(12),fraxin(13),胡萝卜苷(14)。其中,化合物1-8为新化合物,9-11为首次从该植物中分离得到。药理筛选结果表明:化合物1-3有较好的保肝活性,5-6有较好的抗肿瘤活性。
Polyspora chrysandra Cowan.belongs to the family Theaceae,which consists of approximately 520 species categorized under 25 different genera.Although the chemistry and bioactivity of the genus Polyspora has seldom been previously reported, the other species of the family Theaceae have been extensively demonstrated.Theaceae species are widely distributed in tropical and warm temperate areas of the world. Bioactive studies on some members of Theaceae family have shown a wide range of activity,including antitumor,anti-HIV,antibacterial and antifungal.In addition,various plants of this family are used as remedies for rheumatism,swelling,traumatic bleeding, tropical ulcers and sores.
A series of pharmacological experiments and systematic analyses of chemical constitutions in the roots of Polyspora chrysandra Cowan have been conducted in this thesis,which placed a foundation for the further exploiture of Polyspora.The dried roots of Polyspora chrysandra Cowan were refluxed by 95%ethanol and concentrated under reduced pressure,then the residue was extracted with petrol ether,CHCl_3,EtOAc and n-BuOH in sequence.The CHCl_3,EtOAc and water portions showed significant inhibitory effect on GalN-induced liver lesion;The CHCl_3,n-BuOH and water portions showed inhibitory effect on HIV integrase.Based on these results,we studied each extract portion and tried to find some chemical compounds related to above bioactivities.
In this thesis,eighteen compounds were isolated from the EtOAc and n-BuOH portions of the 95%ethanolic extract.And their structures were elucidated by spectroscopic methods including IR,MS,HR-MS,1D and 2D-NMR and chemical experiments.These compounds were determined as:(2R,3R)-3,5,7,4'-tetrahydroxy flavanonol-3-O-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamno pyranoside(1),(2R,3S)-3,5,7,4'-tetrahydroxyflavanonol-3-O-α-L-rhamnopyranosyl (1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamnopyranoside(2),(2S,3S)-3,5,7,4'-tetra hydroxyflavanonol-3-O-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamnopyranoside (3),(2S,3S)-3,5,7,3',5'-penthydroxy flavanonol-3-O-α-L-rham nopyranosyl(1→2)-β-D-glucopyranosyl(1→2)-α-L-rhamnopyranoside(4),16α,28-diol-15α-acetyloxy-22α-angeloyloxy theasapogenol B 3β-O-β-D-galactopyranosyl(1→2)[-β-D-xylopyranosyl(1→2)-α-L-arabinopyranosyl(1→3)]-β-D-glucopyranosid uronic acid(5),16α,28-diol-21β-acetyloxy-22α-angeloyloxy theasapogenol B 3β-O-β-D-galactopyranosyl (1→2)[-β-D-xylopyranosyl(1→2)-α-L-arabinopyranosyl(1→3)]-β-D-glucopyranosiduronic acid(6),16α,28-diol-22α-angeloyloxy theasapogenol B 3β-O-β-D -galactopyranosyl(1→2)[-β-D-xylopyranosyl(1→2)-α-L-arabinopyranosyl(1→3)]-β-D -glucopyranosiduronic acid(7),16α-hydroxy-28-O-glucopyranosyl-theasapogenol B 3-O-α-L-rhamnopyranoside(1→2)-α-L-arabinopyranosyl(1→3)-β-D-glucopyranosiduronic acid(8),3-O-glucopyranosyl-epi-lyoniresinol(9),(-)-lyoniresinol 3-O-β-D-glucopyranoside(10),(+)-lyoniresinol 3-O-β-D-glucopy ranoside(11), leonuriside A(12),fraxin(13) and daucosterin(14).Among them,compounds 1-8 are new compounds,9-11 were isolated from this genus for the frist time.Compounds 1-3 showed remarkable hepatoprotective activity,5-7 showed potent antitumor activity.
引文
1.杨世雄,国产大头茶属的分类处理,热带热亚带植物学报,2005,13(4),363-365。
2.袁丽萍,山茶花总黄酮对实验性心肌缺血的保护作用,中国新药与临床药理,2004,15(1),25-28。
3.罗胜勇,山茶花总黄酮对缺血性脑损伤的保护作用,中国新药与临床药理,2004,15(6),376-379。
4.袁丽萍,山茶花总黄酮对血小板凝集和实验性血栓形成的影响,安徽医科大学学报,2004,39(2),142-143。
5.叶创兴,大头茶族的范围及族内属的界限.广西植物,1990,10(2),99-103。
6.H.M.T.B.Herath et al.Two oleanane triterpenoids from Gordonia ceylanica and their conversions to taraxarane triterpenoids.Phytochemistry,2000,54,823-827.
7.H.M.T.B.Herath et al.A new oleanane triterpenoid from Gordonia ceylanica Natural Product Letters,2001,15(5),339-344.
8.H.M.T.B.Herath et al.Triterpenoids of Gordonia dassanayakei,Natural Product Sciences,2000,6(2),102-105
9.Chyurng Wern Chang,New Pyrone Glucoside,and Dimeric Ellagitannins from Gordonia axillars,Chem.Pharm.Bull.,1999,42(9),1922-1923。
10.H.M.T.B.Herath et al.Antifungal constituent from Gordonia dassanayakei.Fitoterapia,72(5),565-567。
11.William Gaffield,Anthony C.Waiss.Structural Relationships and Interconwersions of Isomeric Astilbins.J.Org.Chem.,1975,40(8),1057-1061。
12.William Gaffield.Absolute Configurations of the cis-Dihydroquercetin-3-O-β-L-Rhamnosides Isoastilbin and Neoisoastilbin.Chem.Pharm.Bull.1975,44(5),1102-1103.
14.Keiichi Nishimura,Triterpenoid Saponins from Ilex kudincha,J.Nat.Prod.,1999,62,1128-1133。
13.Chen T,Li J X,Cai Y,et al.Chinese Chemical Letters,2002,13(6),537-538。
15.Mitsuhiko Miyamura,Seven Aromatic Compounds from Bank of Cinn Amomum Cassia,Phytochemistry,1983,22(1),215-218。
16.Hans Achenbach,New Lignan Glucosides from Stemmadenia minima,Planta Med.1992,58,270-273。
17.Yen Cheng,A Monoterpenoid and two simple phenols from heratwood of Ficus Microcarpa,Phytochemistry,1998,49(8),2417-2419。
18.Ana Crespo Irizar,Constituents of Prunus Spinosa,J.Nat.Products,1992,55(4),450-454。
2.袁丽萍,山茶花总黄酮对实验性心肌缺血的保护作用,中国新药与临床药理,2004,15(1),25-28。
3.罗胜勇,山茶花总黄酮对缺血性脑损伤的保护作用,中国新药与临床药理,2004,15(6),376-379。
4.袁丽萍,山茶花总黄酮对血小板凝集和实验性血栓形成的影响,安徽医科大学学报,2004,39(2),142-143。
5.叶创兴,大头茶族的范围及族内属的界限.广西植物,1990,10(2),99-103。
6.H.M.T.B.Herath et al.Two oleanane triterpenoids from Gordonia ceylanica and their conversions to taraxarane triterpenoids.Phytochemistry,2000,54,823-827.
7.H.M.T.B.Herath et al.A new oleanane triterpenoid from Gordonia ceylanica Natural Product Letters,2001,15(5),339-344.
8.H.M.T.B.Herath et al.Triterpenoids of Gordonia dassanayakei,Natural Product Sciences,2000,6(2),102-105
9.Chyurng Wern Chang,New Pyrone Glucoside,and Dimeric Ellagitannins from Gordonia axillars,Chem.Pharm.Bull.,1999,42(9),1922-1923。
10.H.M.T.B.Herath et al.Antifungal constituent from Gordonia dassanayakei.Fitoterapia,72(5),565-567。
11.William Gaffield,Anthony C.Waiss.Structural Relationships and Interconwersions of Isomeric Astilbins.J.Org.Chem.,1975,40(8),1057-1061。
12.William Gaffield.Absolute Configurations of the cis-Dihydroquercetin-3-O-β-L-Rhamnosides Isoastilbin and Neoisoastilbin.Chem.Pharm.Bull.1975,44(5),1102-1103.
14.Keiichi Nishimura,Triterpenoid Saponins from Ilex kudincha,J.Nat.Prod.,1999,62,1128-1133。
13.Chen T,Li J X,Cai Y,et al.Chinese Chemical Letters,2002,13(6),537-538。
15.Mitsuhiko Miyamura,Seven Aromatic Compounds from Bank of Cinn Amomum Cassia,Phytochemistry,1983,22(1),215-218。
16.Hans Achenbach,New Lignan Glucosides from Stemmadenia minima,Planta Med.1992,58,270-273。
17.Yen Cheng,A Monoterpenoid and two simple phenols from heratwood of Ficus Microcarpa,Phytochemistry,1998,49(8),2417-2419。
18.Ana Crespo Irizar,Constituents of Prunus Spinosa,J.Nat.Products,1992,55(4),450-454。