儿茶化学成分及生物活性研究
摘要
金合欢属(Acacia)植物为豆科植物,有1200多种植物,分布在全世界的各个地区,是豆科中的第二大属,其中将近800种分布在澳大利亚,130种在非洲。20种在印度,一小部分在亚洲,还有一些在西北半球。中药儿茶(Acacia catechu)为豆科植物儿茶A. catechu(L.)的去皮枝、干的干燥浸膏。儿茶在我国应用广泛,在民间主要用于湿疹,口疮,跌打损伤,外伤出血等。本文对购于北京同仁堂药店的中药儿茶进行了化学成分和生物活性研究。
采用多种色谱方法(硅胶色谱、大孔树脂、ODS色谱、MCI色谱)从儿茶水浸膏得到了21个化合物,并运用波谱技术(IR,UV, MS,1D-NMR,2D-NMR和CD)鉴定了它们的化学结构。21个化合物分别是4-hydroxybenzoic acid(1)、kaempferol(2)、quercetin(3)、3,4',7-trihydroxyl-3,5-dimethoxyflavone(4)、catechin (5)、epicatechin(6)、afzelechin(7)、epiafzelechin(8)、mesquitol(9)、ophioglonin(10)、aromadendrin(11)、phenol(12)、N-tetratriacontane(13)、4-hydroxyp henylethanol (14)、3,3',5,5',7-pentahydroxyflavanone(15)、3,3',4',7-tetra hydroxyflavanone (16)、3,3', 4',5—tetrahydroxy-7-methoxyflavonoid(17)、5-hydroxy-2-[2-(4-hydroxy phenyl)acetyl]-3-methoxybenzoic acid(18)、(2 S,3 S)-3,3',4',7,8-pentahydroxy flavane(19)、(3 R, 4R)-3-(3,4-dihydroxyphenyl)-4-hydroxy cyclohexanone(20)和(4R)-5-[1-(3,4-dihydro phenyl)-3-oxobutyl]-dihydrofuran-2(3 H)-one(21)。其中化合物18-21为新化合物,化合物4、9、10首次从该属植物中分离得到。
药理筛选实验表明,儿茶水提物的乙酸乙酯部位有显著的升白作用,对乙酸乙酯中分离的化合物5、6进行了体内升高白细胞实验,其中化合物6具有较强的升高白细胞活性；并对新化合物进行了抗自由基活性筛选,化合物18-21均有显著的体外清除ONOO-的活性,同时,化合物19还具有显著的体外清除DPPH的活性。
Acacia is the second largest genus in the Leguminosae family, comprising more than 1200 species worldwide, with members found in almost all habitats. Out of 1200 Acacia species, approximately 800 are found in Australia,130 in Africa,20 in India, a smaller number in Asia, and the remaining specieses in the New World.
Traditional Chinese medicine for Acacia catechu (L.) is the dry extract of the peeled branches of A. catechu. A. catechu is widely used in China. It was used as folk medicine to treat eczema, mouth sores, bruises, traumatic bleeding and so on. The chemical constituents and bioactivities of A. catechu were studied, which was purchased from Beijing Tongrentang Pharmacy.
In the course of our search for active compounds from water extract of medical A. catechu,21 compounds were isolated by chromatographed columns of silica gel, macroporous resin, ODS and MCI gel. Their structures were elucidated by analysis of several spectra such as UV, IR, MS,1D-NMR,2D-NMR and CD, as 4-hydroxybenzoic acid (1), kaempferol (2), quercetin (3),3,4',7-trihydroxyl-3,5-dimethoxyflavone (4), catechin (5), epicatechin (6), afzelechin (7), epiafzelechin (8), mesquitol (9), ophioglonin (10), aromadendrin (11), phenol (12), N-tetratriacontane (13),4-hydroxyp henylethanol(14),3,3',5,5',7-pentahydroxyflavanone (15),3,3',4',7-tetra hydroxyflavanone(16),3,3',4',5—tetrahydroxy-7-methoxyflavonoid(17),5-hydroxy-2-[2-(4-hydroxyphenyl)acetyl]-3-methoxybenzoic acid (18), (2 S,3 S)-3,3',4',7, 8-pentahydroxyflavane (19), (3 R,4 R)-3-(3,4-dihydroxyphenyl)-4-hydroxy cyclo hexanone (20), (4 R)-5-[1-(3,4-dihydrophenyl)-3-oxobutyl]-dihydrofuran-2(3 H)-one (21). Among these, compounds 4,9,10 are new compounds, compounds 18-21 are first reported from genus Acacia.
The pharmacological experiment indicated the EtOAc fractions of water extract possessed significant leukogenic effect. We did leukogenic experiment with compound 5 and 6, wherein compound 6 showed significant leukogenic effect. In addition, new compounds 18-21 were evaluated in vivo free-radical scavenging effects. It was found that the four new compounds presented a remarkable capacity to scanvenge peroxynitrite. Meantime, compound 19 had an outstanding scavenging effect of stable DHHP free radical.
采用多种色谱方法(硅胶色谱、大孔树脂、ODS色谱、MCI色谱)从儿茶水浸膏得到了21个化合物,并运用波谱技术(IR,UV, MS,1D-NMR,2D-NMR和CD)鉴定了它们的化学结构。21个化合物分别是4-hydroxybenzoic acid(1)、kaempferol(2)、quercetin(3)、3,4',7-trihydroxyl-3,5-dimethoxyflavone(4)、catechin (5)、epicatechin(6)、afzelechin(7)、epiafzelechin(8)、mesquitol(9)、ophioglonin(10)、aromadendrin(11)、phenol(12)、N-tetratriacontane(13)、4-hydroxyp henylethanol (14)、3,3',5,5',7-pentahydroxyflavanone(15)、3,3',4',7-tetra hydroxyflavanone (16)、3,3', 4',5—tetrahydroxy-7-methoxyflavonoid(17)、5-hydroxy-2-[2-(4-hydroxy phenyl)acetyl]-3-methoxybenzoic acid(18)、(2 S,3 S)-3,3',4',7,8-pentahydroxy flavane(19)、(3 R, 4R)-3-(3,4-dihydroxyphenyl)-4-hydroxy cyclohexanone(20)和(4R)-5-[1-(3,4-dihydro phenyl)-3-oxobutyl]-dihydrofuran-2(3 H)-one(21)。其中化合物18-21为新化合物,化合物4、9、10首次从该属植物中分离得到。
药理筛选实验表明,儿茶水提物的乙酸乙酯部位有显著的升白作用,对乙酸乙酯中分离的化合物5、6进行了体内升高白细胞实验,其中化合物6具有较强的升高白细胞活性；并对新化合物进行了抗自由基活性筛选,化合物18-21均有显著的体外清除ONOO-的活性,同时,化合物19还具有显著的体外清除DPPH的活性。
Acacia is the second largest genus in the Leguminosae family, comprising more than 1200 species worldwide, with members found in almost all habitats. Out of 1200 Acacia species, approximately 800 are found in Australia,130 in Africa,20 in India, a smaller number in Asia, and the remaining specieses in the New World.
Traditional Chinese medicine for Acacia catechu (L.) is the dry extract of the peeled branches of A. catechu. A. catechu is widely used in China. It was used as folk medicine to treat eczema, mouth sores, bruises, traumatic bleeding and so on. The chemical constituents and bioactivities of A. catechu were studied, which was purchased from Beijing Tongrentang Pharmacy.
In the course of our search for active compounds from water extract of medical A. catechu,21 compounds were isolated by chromatographed columns of silica gel, macroporous resin, ODS and MCI gel. Their structures were elucidated by analysis of several spectra such as UV, IR, MS,1D-NMR,2D-NMR and CD, as 4-hydroxybenzoic acid (1), kaempferol (2), quercetin (3),3,4',7-trihydroxyl-3,5-dimethoxyflavone (4), catechin (5), epicatechin (6), afzelechin (7), epiafzelechin (8), mesquitol (9), ophioglonin (10), aromadendrin (11), phenol (12), N-tetratriacontane (13),4-hydroxyp henylethanol(14),3,3',5,5',7-pentahydroxyflavanone (15),3,3',4',7-tetra hydroxyflavanone(16),3,3',4',5—tetrahydroxy-7-methoxyflavonoid(17),5-hydroxy-2-[2-(4-hydroxyphenyl)acetyl]-3-methoxybenzoic acid (18), (2 S,3 S)-3,3',4',7, 8-pentahydroxyflavane (19), (3 R,4 R)-3-(3,4-dihydroxyphenyl)-4-hydroxy cyclo hexanone (20), (4 R)-5-[1-(3,4-dihydrophenyl)-3-oxobutyl]-dihydrofuran-2(3 H)-one (21). Among these, compounds 4,9,10 are new compounds, compounds 18-21 are first reported from genus Acacia.
The pharmacological experiment indicated the EtOAc fractions of water extract possessed significant leukogenic effect. We did leukogenic experiment with compound 5 and 6, wherein compound 6 showed significant leukogenic effect. In addition, new compounds 18-21 were evaluated in vivo free-radical scavenging effects. It was found that the four new compounds presented a remarkable capacity to scanvenge peroxynitrite. Meantime, compound 19 had an outstanding scavenging effect of stable DHHP free radical.
引文
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[2]A. H. Gaara, M. I. Nassar, M. Younis, G. A. Elmgeed, T. J. Mabry, P. W. Pare. Biological active polyphenolic compounds from Acacia ehrenbergiana[J]. Rev. Latinoamer. Quim,2008,36(2):52-59.
[3]D. Shen, Q. Wu, M. Wang, Y. Yang, E. J. Lavoie, J. E. Simon. Determination of predominant catechins in Acacia catechu by liquid chromatography/electrospray ionization-mass spectrometry[J]. J. Agric. Food Chem.,2006,54:3219-3224.
[4]E. Malan, D. H. Pienaar. (+)-Catechin-galloyl esters from the bark of Acacia gerrardii[J]. Phytochemistry,1987,25(1):2049-2051.
[5]A. Cronje, J. P. Steynberg, E. V. Brandt, D. A. Young, D. Ferreira. Oligomeric flavanoids. Part 16. Novel prorobinetinidins and the first A-type proanthocyanidin with a 5-deoxy A-and a 3,4-cis C-Ring from the Maiden investigation of commercial Wattle Bark Extract[J]. J. Chem. Soc. Trans.1,1993:2467-2477.
[6]E. Malan, D. G. Roux, Flavonoids and tannins of Acacia species[J]. Phytochemistry, 1975,14:1835-1841.
[7]E. Malan, A. Sireeparsad. The structure and synthesis of the first dimeric proteracacindins from Acacia galpinii[J]. Phytochemistry,1995,38(1):237-239.
[8]L. Y. Foo. A novel pyrogallol A-ring proanthocyanidin dimmer from Acacia melanoxylon[J]. J. Chem.Soc., Chem. Commun.,1986:236-237.
[9]V. H. Deshpande, A. D. Patil, Flavonoids of Acacia catechu heartwood[J]. Indian J. Chem.,1981,20B,7:628.
[10]E. Malan. A(4β→5)-linked proteracacinidin dimmer from the heartwood of Acacia caffra[J]. Phytochemistry,1995:1519-1521.
[11]S. E. Drewes, A. H. Ilsley. Isomeric leucofisetinidns from Acacia mearnsii[J]. Phytochemistry,1969,8:1039-1042.
[12]R. Sahai, S. K. Agarwal, R. P. Rastogi. Auriculoside, a new flavan glycoside from Acacia auriculiformis[J]. Phytochemistry,1980,19:1560-1562.
[13]E. V. Brandt, D. G. Roux. Metabolities from the purple heartwood of mimosoideae I, Acacia peuce F. Muell:The first natural 2,3-cis-peltogynoids[J]. J. C. S. Perkin I,1979:777-780.
[14]L. Y. Foo. Configuration and conformation of dihydroflavonols from Acacia melanoxylon[J]. Phytochemistry,26(3),1987:813-817.
[15]H. I. E. Sissi, M. A. E. Ansari, S. I. E. Negoumy. Phenolics of Acacia farnesiana[J]. Phytochemistry,1973,12:2303.
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