姜黄的化学成分研究
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摘要
姜黄为姜科姜黄属(Curcuma)多年生草本植物姜黄(Curcuma longa L.)的干燥根茎,全世界有50种,中国有16种,产于广西南部至东南部,具有破血行气止痛通经之功效,对姜黄药用有效成分进行提取分离和结构鉴定,有利于其药用资源的深层次开发,提高其药用价值。
利用硅胶、ODS、凝胶柱色谱等分离方法对姜黄的95%乙醇(体积分数)提取物进行了化学成分分离鉴定,从中分离得到了14个化合物,通过理化性质以及波谱手段(NMR),鉴定了其中13个化合物的结构,分别为:姜黄素(curcumin,1)、β-谷甾醇(β-sitosterol,2)、琥珀酸(Butanedioic acid,3)、丁烯醛(crotonaldehyde,4)、1,7-dichlorol-isopropyl-4,7-dimethylperhydronaphthalene(isozingiberene dihydrochloride,5)、姜酮(Gingerdione,6)、3,3,5-三甲基-4-对甲基-苯基4-羟基-环己酮(3,3,5-trimethyl-4-(p-methyl)-phenyl-4-hydroxy-hextone,7)、双去甲氧基姜黄素(bisdemethoxycurcumin,8)、单去甲氧基姜黄素(demethoxycurcumin,9)、N,N-二甲基苯甲醛(4-(dimethylamino)-Benzaldehyde,10)、原儿茶酸(protocatechuic acid 11)、胡萝卜苷(daucosterol,12)、蔗糖(sucrose,13)。其中化合物5为一个新天然产物,化合物7为一个新化合物。
The traditional Chinese medicine Curcuma longa is a member of the Ginger family.There are fifty kinds specices in the word,and only sixteen kinds were planted in China,mainly in Guang Xi province.It has been used in folk medicines as a toxinicide.For the purpose of finding much more bioactive agents from this plant and to supply its exploitation,the further chemical study of this plant was carried out.
By mean of many kinds of isolation methods,such as Silica gel,Sephadex LH-20 and so on, the shade-dried roots of Curcuma longa(5 kg)were bladed and extracted with 95%ethanol and 14 compounds were isolated from this fraction.The structures of 13 compounds were identified by their physico-chemical characteristics and spectra data,and they were identified as curcumin(1),β-sitosterol(2),Butanedioic acid(3),crotonaldehyde(4), 1,7-dichlorol-isopropyl-4,7-dimethylperhydronaphthalene(isozingiberene dihydrochloride) (5),Gingerdione(6),(3,3,5-trimethyl-4-p-methyl-phenyl-4-hydroxyl-hextone,7), bisdemethoxycurcumin(8),demethoxycurcumin(9),(4-(dimethyla- mino)-Benzaldehyde (10),protocatechuic acid(11),daucosterol(12),sucrose(13)respectively.Among them compound 5 was a novel natural product,while compound 7 was a novel compound.
利用硅胶、ODS、凝胶柱色谱等分离方法对姜黄的95%乙醇(体积分数)提取物进行了化学成分分离鉴定,从中分离得到了14个化合物,通过理化性质以及波谱手段(NMR),鉴定了其中13个化合物的结构,分别为:姜黄素(curcumin,1)、β-谷甾醇(β-sitosterol,2)、琥珀酸(Butanedioic acid,3)、丁烯醛(crotonaldehyde,4)、1,7-dichlorol-isopropyl-4,7-dimethylperhydronaphthalene(isozingiberene dihydrochloride,5)、姜酮(Gingerdione,6)、3,3,5-三甲基-4-对甲基-苯基4-羟基-环己酮(3,3,5-trimethyl-4-(p-methyl)-phenyl-4-hydroxy-hextone,7)、双去甲氧基姜黄素(bisdemethoxycurcumin,8)、单去甲氧基姜黄素(demethoxycurcumin,9)、N,N-二甲基苯甲醛(4-(dimethylamino)-Benzaldehyde,10)、原儿茶酸(protocatechuic acid 11)、胡萝卜苷(daucosterol,12)、蔗糖(sucrose,13)。其中化合物5为一个新天然产物,化合物7为一个新化合物。
The traditional Chinese medicine Curcuma longa is a member of the Ginger family.There are fifty kinds specices in the word,and only sixteen kinds were planted in China,mainly in Guang Xi province.It has been used in folk medicines as a toxinicide.For the purpose of finding much more bioactive agents from this plant and to supply its exploitation,the further chemical study of this plant was carried out.
By mean of many kinds of isolation methods,such as Silica gel,Sephadex LH-20 and so on, the shade-dried roots of Curcuma longa(5 kg)were bladed and extracted with 95%ethanol and 14 compounds were isolated from this fraction.The structures of 13 compounds were identified by their physico-chemical characteristics and spectra data,and they were identified as curcumin(1),β-sitosterol(2),Butanedioic acid(3),crotonaldehyde(4), 1,7-dichlorol-isopropyl-4,7-dimethylperhydronaphthalene(isozingiberene dihydrochloride) (5),Gingerdione(6),(3,3,5-trimethyl-4-p-methyl-phenyl-4-hydroxyl-hextone,7), bisdemethoxycurcumin(8),demethoxycurcumin(9),(4-(dimethyla- mino)-Benzaldehyde (10),protocatechuic acid(11),daucosterol(12),sucrose(13)respectively.Among them compound 5 was a novel natural product,while compound 7 was a novel compound.
引文
[1]贵州植物志编辑委员会.贵州植物志(第四卷)[M].成都.四川民族出版社.1989.
[2][明]李时珍.本草纲目(校点本)[M].第2册.北京:人民卫生出版社,1979:880
[3]王贤纯,谢锦云.姜黄的综合利用[J].食品科学,1993,164(8):49-51.
[4]Conney AH,Lou YR,Osawa T,et al.Some perspectives on dietary inhibition of carcinogenesis:studies with curcumin and tea[J].Proc.Soc.Exp.Biol.&Med.,1997,216(2):234-245.
[5]Ghatak N,Basu N.Sodium curcuminate as an effective anti-inflammatory agent[J].Indian J.Exp.Boil,1972,10(3):235-236.
[6]Srimal RC,Dhawan BN.In:Development of Unani drugs from herbal sources and the role of elements in their mechanism of action,(Arora BB,ed.).Hamdard National Foundation Monograph,New Delhi,India.
[7]Chandra D,Gupta SS.Anti-inflammatory and anti-arthritic activity of volatile oil of Curcuma longa(Haldi)[J].Indian J.Med.Res.,1972,60(1):138-42.
[8]Arora RB,Kapoor V,Basu N,et al.Anti-inflammatory studies on Curcuma longa(turmefic)[J].Indian J.Med.Res.,1971,59(8):1289-1295.
[9]Sharm OP.Antioxidant activity of curcumin and related compounds[J].Biochem Pharmacol.1976,25:1181-1182.
[10]Yegnanarayan R,Saraf AP,Balwani JH.Comparison of anti-inflammatory activity of various extracts of Curcuma longa(Linn)[J].Indian J.Med.Res.,1976,64(4):601-608.
[11]Ramprasad C,Sirsi M.Observation on the Pharmacology of Curcuma Longa:Effect of Curcumin and Essential Oil of Curcuma Longa on Bile Secretion[J].J Sci Industr Res.,1956,15C:262-265.
[12]Hussain M.S,Chandrasekhara N.Effect of curcumin and capsaicin on the regression of pre-established cholesterol gallstones in mice[J].Nutri.Res.1994,14(10):1561-1574.
[13] Hussain M S, Chandrasekhara N. Effect on curcumin on cholesterol gall-stone induction in mice[J]. Ind J Med Res. 1992, 96: 288-291.
[14] Hussain MS, Chandrasekhara N. Influence of curcumin and capsaicin on cholesterol gallstone induction in hamsters and mice[J]. Nutri. Res. 1993, 13(3): 349-357.
[15] Sakai K, Miyazaki Y, Yamane T, et al. Effect of extracts of Zingiberaceae herbs on gastric secretion in rabbits[J]. Chem. Pharm. Bull. 1989, 37(1): 215-217.
[16] Rao TS Basu N, Siddiqui HH. Anti-inflammatory activity of curcumin analogues[J]. Indian J. Med. Res., 1982, 75: 574-8.
[17] Rafatullah S, Tariq M, Al-Yahya MA, et al. Evaluation of turmeric (Curcuma longa) for gastric and duodenal antiulcer activity in rats [J]. J. Ethnopharmacol, 1990, 29(1): 25-34.
[18] Gupta B, Kulshrestha VK, Srivastava RK, et al. Mechanisms of curcumin induced gastric ulcer in rats[J]. Indian J Med Res, 1980, 71(5):806-814.
[19] Soni KB, Lahiri M, Chackradeo P, et al. Protective effect of food additives on aflatoxin-induced mutagenicity and hepatocarcinogenicity[J]. Cancer Lett., 1997: 115(2): 129-133.
[20] Goud VK, Polasa K, Krishnaswamy K. Effect of turmeric on xenobiotic metabolising enzymes[J]. Plants Food for Human Nutri., 1993,44(1):87-92.
[21] Singh A, Singh SP, Bamezai R. Postnatal modulation of hepatic biotransformation system enzymes via translactational exposure of Fl mouse pups to turmeric and curcumin[J]. Cancer Lett. 1995, 96(1): 87-93.
[22] Oetari S, Sudibyo M, Commandeur JN, et al. Effects of curcumin on cytochrome P450 and glutathione S-transferase activities in rat liver[J]. Biochem Pharmacol, 1996, 51(1):39-45.
[23] Venkatesan N. Chandrakasan G. Modulation of cyclophosphamide-induced early lung injury by curcumin, an anti-inflammatory antioxidant[J]. Mol Cellular Biochem., 1995,142(1): 79-87.
[24]陈文娟.姜黄素对恶性肿瘤细胞的调控[J].临床血液学杂志,1999,12(5):238.
[25]Ramirez MC,Mesa MD.Oral administration of a turmeric extract inhibits LDL oxidation and has hypocholesterolemic effects in rabbits with experimental atterosclerosis[J].Atherosclerosis,1999,147(2):371.
[26]Srivastava R,Dikshit M,Srimal RC,et al.Anti-thrombotic effect of curcumin[J].Thromb.Res.1985,40(3):413-417.
[27]科技部,国家计委,国家药监局 等.中药现代化发展纲要,2002
[28]Mulky N,Amonkar AJ,Bhide SV.Antimutagenicity of curcumins and related compounds:the structural requirement for the antimutagenicity of curcumins[J].India Drug,1987,25(3):91-95.
[29]South EH,Exon JH,Hendrix K.Dietary curcumin enhances antibody response in rats[J].Immunopharrnacol Immunotoxicol.,1997,19(1):105-119.
[30]Yang F.,Lim GP,Begum AN,et al.Curcumin inhibits formation of amyloid beta oligomers and fibrils,binds plaques,and reduces amyloid in vivo[J].J Biol Chem.2005,280(7):5892-5901.
[31]Rasmussen HB,Christensen SB,Kvist LP,et al.A simple and efficient separation of the curcumins,the antiprotozoal constituents of Curcuma longa[J].Planta med.2000,66(4):396-398.
[32]Vanisree AJ,Sudha N.Curcumin combats against cigarette smoke and ethanol-induced lipid alterations in rat lung and liver[J].Mol Cell Biochem.2006,288(1-2):115-123.
[33]DeQuan Yu,《Analyt Chem Handbook》.Vol:5.Beijing:chemistry industry publishing house,1989:507.
[34]The Sadtler Standard Spectra.11335.
[35]《高分子学报》,2001,4:466-470.
[36]Food Research International 2005:38(8-9),1039-1044.
[37]Biochimica et Biophysica Acta.2006:70-77.
[38]吴宇雄,周尽花.对二甲氨基苯甲醛研究[J].云南化工,2005,32(3):20
[2][明]李时珍.本草纲目(校点本)[M].第2册.北京:人民卫生出版社,1979:880
[3]王贤纯,谢锦云.姜黄的综合利用[J].食品科学,1993,164(8):49-51.
[4]Conney AH,Lou YR,Osawa T,et al.Some perspectives on dietary inhibition of carcinogenesis:studies with curcumin and tea[J].Proc.Soc.Exp.Biol.&Med.,1997,216(2):234-245.
[5]Ghatak N,Basu N.Sodium curcuminate as an effective anti-inflammatory agent[J].Indian J.Exp.Boil,1972,10(3):235-236.
[6]Srimal RC,Dhawan BN.In:Development of Unani drugs from herbal sources and the role of elements in their mechanism of action,(Arora BB,ed.).Hamdard National Foundation Monograph,New Delhi,India.
[7]Chandra D,Gupta SS.Anti-inflammatory and anti-arthritic activity of volatile oil of Curcuma longa(Haldi)[J].Indian J.Med.Res.,1972,60(1):138-42.
[8]Arora RB,Kapoor V,Basu N,et al.Anti-inflammatory studies on Curcuma longa(turmefic)[J].Indian J.Med.Res.,1971,59(8):1289-1295.
[9]Sharm OP.Antioxidant activity of curcumin and related compounds[J].Biochem Pharmacol.1976,25:1181-1182.
[10]Yegnanarayan R,Saraf AP,Balwani JH.Comparison of anti-inflammatory activity of various extracts of Curcuma longa(Linn)[J].Indian J.Med.Res.,1976,64(4):601-608.
[11]Ramprasad C,Sirsi M.Observation on the Pharmacology of Curcuma Longa:Effect of Curcumin and Essential Oil of Curcuma Longa on Bile Secretion[J].J Sci Industr Res.,1956,15C:262-265.
[12]Hussain M.S,Chandrasekhara N.Effect of curcumin and capsaicin on the regression of pre-established cholesterol gallstones in mice[J].Nutri.Res.1994,14(10):1561-1574.
[13] Hussain M S, Chandrasekhara N. Effect on curcumin on cholesterol gall-stone induction in mice[J]. Ind J Med Res. 1992, 96: 288-291.
[14] Hussain MS, Chandrasekhara N. Influence of curcumin and capsaicin on cholesterol gallstone induction in hamsters and mice[J]. Nutri. Res. 1993, 13(3): 349-357.
[15] Sakai K, Miyazaki Y, Yamane T, et al. Effect of extracts of Zingiberaceae herbs on gastric secretion in rabbits[J]. Chem. Pharm. Bull. 1989, 37(1): 215-217.
[16] Rao TS Basu N, Siddiqui HH. Anti-inflammatory activity of curcumin analogues[J]. Indian J. Med. Res., 1982, 75: 574-8.
[17] Rafatullah S, Tariq M, Al-Yahya MA, et al. Evaluation of turmeric (Curcuma longa) for gastric and duodenal antiulcer activity in rats [J]. J. Ethnopharmacol, 1990, 29(1): 25-34.
[18] Gupta B, Kulshrestha VK, Srivastava RK, et al. Mechanisms of curcumin induced gastric ulcer in rats[J]. Indian J Med Res, 1980, 71(5):806-814.
[19] Soni KB, Lahiri M, Chackradeo P, et al. Protective effect of food additives on aflatoxin-induced mutagenicity and hepatocarcinogenicity[J]. Cancer Lett., 1997: 115(2): 129-133.
[20] Goud VK, Polasa K, Krishnaswamy K. Effect of turmeric on xenobiotic metabolising enzymes[J]. Plants Food for Human Nutri., 1993,44(1):87-92.
[21] Singh A, Singh SP, Bamezai R. Postnatal modulation of hepatic biotransformation system enzymes via translactational exposure of Fl mouse pups to turmeric and curcumin[J]. Cancer Lett. 1995, 96(1): 87-93.
[22] Oetari S, Sudibyo M, Commandeur JN, et al. Effects of curcumin on cytochrome P450 and glutathione S-transferase activities in rat liver[J]. Biochem Pharmacol, 1996, 51(1):39-45.
[23] Venkatesan N. Chandrakasan G. Modulation of cyclophosphamide-induced early lung injury by curcumin, an anti-inflammatory antioxidant[J]. Mol Cellular Biochem., 1995,142(1): 79-87.
[24]陈文娟.姜黄素对恶性肿瘤细胞的调控[J].临床血液学杂志,1999,12(5):238.
[25]Ramirez MC,Mesa MD.Oral administration of a turmeric extract inhibits LDL oxidation and has hypocholesterolemic effects in rabbits with experimental atterosclerosis[J].Atherosclerosis,1999,147(2):371.
[26]Srivastava R,Dikshit M,Srimal RC,et al.Anti-thrombotic effect of curcumin[J].Thromb.Res.1985,40(3):413-417.
[27]科技部,国家计委,国家药监局 等.中药现代化发展纲要,2002
[28]Mulky N,Amonkar AJ,Bhide SV.Antimutagenicity of curcumins and related compounds:the structural requirement for the antimutagenicity of curcumins[J].India Drug,1987,25(3):91-95.
[29]South EH,Exon JH,Hendrix K.Dietary curcumin enhances antibody response in rats[J].Immunopharrnacol Immunotoxicol.,1997,19(1):105-119.
[30]Yang F.,Lim GP,Begum AN,et al.Curcumin inhibits formation of amyloid beta oligomers and fibrils,binds plaques,and reduces amyloid in vivo[J].J Biol Chem.2005,280(7):5892-5901.
[31]Rasmussen HB,Christensen SB,Kvist LP,et al.A simple and efficient separation of the curcumins,the antiprotozoal constituents of Curcuma longa[J].Planta med.2000,66(4):396-398.
[32]Vanisree AJ,Sudha N.Curcumin combats against cigarette smoke and ethanol-induced lipid alterations in rat lung and liver[J].Mol Cell Biochem.2006,288(1-2):115-123.
[33]DeQuan Yu,《Analyt Chem Handbook》.Vol:5.Beijing:chemistry industry publishing house,1989:507.
[34]The Sadtler Standard Spectra.11335.
[35]《高分子学报》,2001,4:466-470.
[36]Food Research International 2005:38(8-9),1039-1044.
[37]Biochimica et Biophysica Acta.2006:70-77.
[38]吴宇雄,周尽花.对二甲氨基苯甲醛研究[J].云南化工,2005,32(3):20