姜黄醇提物化学成分及其抗氧化活性分析
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摘要
目的:研究姜黄(Curcuma longa L.)的化学成分及其抗氧化活性。方法:应用硅胶柱色谱、Sephadex LH-20凝胶柱色谱以及高效液相制备色谱等方法进行分离纯化,根据高分辨质谱、核磁共振谱鉴定化合物的结构;同时采用1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picrylhydrazyl,DPPH)法、2,2’-联氮双(3-乙基苯并噻唑啉-6-磺酸)(2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid),ABTS)法和铁氰化钾还原法对分离得到的化合物进行抗氧化活性筛选。结果:从姜黄中分离鉴定了7个合物,分别为Zingerol(1)、Dihydroferulic acid ethyl ester(2);乙基-3-(4-羟基-苯基)-丙酸乙酯(3)、Zingerone dimer [4,4’-(6,6’-dihydroxy-5,5’-dimethoxy-[1,1’-biphenyl]-3,3’-diyl)bis(butan-2-one)](4)、姜酮(5)、4-(3,4-二甲氧基苯基)丁烷-2-酮(6)、香草醛(7)。其中,化合物1～5均具有一定的抗氧化活性,ABTS阳离子自由基清除实验中,化合物1和化合物2的IC50值分别为(3±0.2)μmol/L和(12±1.0)μmol/L,化合物1优于阳性对照VC(VC的IC50值(13±1.1)μmol/L),化合物2与VC效果相当,还原力实验中,化合物1活性优于VC,浓度低于0.125μmol/mL时化合物2活性强于VC。结论:化合物4为新的天然产物,化合物1、2、3和6为姜黄属中首次发现,化合物1抗氧化活性较强可能与其脂肪链2位上羟基取代有关,姜黄醇提物中的酚类成分是姜黄抗氧化活性的物质基础之一。
Objective: To identify the chemical constituents from the rhizome of Curcuma longa L. and to assess their antioxidant activity. Methods: The chemical constituents were purified consecutively by silica gel column chromatography, Sephadex LH-20 gel column chromatography, and preparative high performance liquid chromatography(HPLC). Their structures were identified by spectroscopic analyses, and their antioxidant activity were evaluated by 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate)(ABTS) radical cation scavenging, 1,1-diphenyl-2-picrylhydrazyl(DPPH) radical scavenging, and potassium ferricyanide reduction assays. Results: Seven compounds were isolated from C. longa L. and were identified as zingerol(1), dihydroferulic acid ethyl ester(2), ethyl 3-(4-hydroxy-phenyl)-propionate(3), zingerone dimer [4,4'-(6,6'-dihydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-3,3'-diyl)bis(butan-2-one)](4), zingiberone(5), 4-(3,4-dimethoxyphenyl)butan-2-one(6), and vanillin(7). Among them, compounds 1–5 showed antioxidant activity. The IC50 of compounds 1 and 2 were(3 ± 0.2) and(12 ± 1.0) μmol/L, respectively, in ABTS assay. Compound 1 was found to exhibit higher antioxidant activity than the positive drug, VC(VC, IC50 value =(13 ± 1.1) μmol/L), while the activity of compound 2 was equivalent to VC. In the reducing power assay, compound 1 showed higher activity than VC at all investigated concentrations, while compound 2 had higher activity than VC only when the concentration was lower than 0.125 μmol/mL. Conclusion: Compound 4 is a new natural product, and compounds 1, 2, 3 and 6 are found from this plant for the first time. The stronger antioxidant activity of compound 1 may be related to hydroxyl substitution at C-2, In addition, the phenols from the ethanol extract may be one of the material bases for the antioxidant activity of C. longa L..
Objective: To identify the chemical constituents from the rhizome of Curcuma longa L. and to assess their antioxidant activity. Methods: The chemical constituents were purified consecutively by silica gel column chromatography, Sephadex LH-20 gel column chromatography, and preparative high performance liquid chromatography(HPLC). Their structures were identified by spectroscopic analyses, and their antioxidant activity were evaluated by 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate)(ABTS) radical cation scavenging, 1,1-diphenyl-2-picrylhydrazyl(DPPH) radical scavenging, and potassium ferricyanide reduction assays. Results: Seven compounds were isolated from C. longa L. and were identified as zingerol(1), dihydroferulic acid ethyl ester(2), ethyl 3-(4-hydroxy-phenyl)-propionate(3), zingerone dimer [4,4'-(6,6'-dihydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-3,3'-diyl)bis(butan-2-one)](4), zingiberone(5), 4-(3,4-dimethoxyphenyl)butan-2-one(6), and vanillin(7). Among them, compounds 1–5 showed antioxidant activity. The IC50 of compounds 1 and 2 were(3 ± 0.2) and(12 ± 1.0) μmol/L, respectively, in ABTS assay. Compound 1 was found to exhibit higher antioxidant activity than the positive drug, VC(VC, IC50 value =(13 ± 1.1) μmol/L), while the activity of compound 2 was equivalent to VC. In the reducing power assay, compound 1 showed higher activity than VC at all investigated concentrations, while compound 2 had higher activity than VC only when the concentration was lower than 0.125 μmol/mL. Conclusion: Compound 4 is a new natural product, and compounds 1, 2, 3 and 6 are found from this plant for the first time. The stronger antioxidant activity of compound 1 may be related to hydroxyl substitution at C-2, In addition, the phenols from the ethanol extract may be one of the material bases for the antioxidant activity of C. longa L..
引文
[1]黄韵璇,李海峰,黄泽波.天然药物抗氧化活性物质研究进展[J].广东药学院学报,2016, 32(4):532-536. DOI:10.16809/j.cnki.1006-8783.2016041803.
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[12]鲁玉妙,马惠玲.植物多酚SCI文献计量及生物活性研究热点分析[J].食品科学,2013, 34(23):375-383. DOI:10.7506/spkx1002-6630-201323074.
[13]赵秀玲.姜黄的化学成分、药理作用及其资源开发的研究进展[J].中国调味品,2012, 37(5):9-13. DOI:10.3969/j.issn.1000-9973.2012.05.003.
[14]赵革平,洪行球,李万里,等.姜黄醇提取物对抗体外LDL氧化修饰作用的研究[J].浙江中医学院学报,1999, 23(2):27-28.DOI:10.16466/j.issn1005-5509.1999.02.015.
[15]曾维才,石碧.天然产物抗氧化活性的常见评价方法[J].化工进展,2013,32(6):1205-1213.DOI:10.3969/j.issn.1000-6613.2013.06.001.
[16]马龙利,李岗,叶菲菲,等.6-姜酚的分离纯化及抗氧化能力研究[J].食品科技,2016, 41(8):206-209. DOI:10.13684/j.cnki.spkj.2016.08.048.
[17]陈洪璋,李伟,肖苏尧,等.桉叶提取物中抗氧化活性物分离纯化、结构鉴定及其活性的研究[J].现代食品科技,2018, 34(4):94-102.DOI:10.13982/j.mfst.1673-9078.2018.04.016.
[18] TAKASHI K,SACHIKO I,KAORU N,et al.Asymmetric synthesis of enantiomerically pure zingerols by lipase-catalyzed transesterification and efficient synthesis of their analogues[J]. Tetrahedron Asymmetry,2013,24(11):621-627.DOI:10.1016/j.tetasy.2013.04.013.
[19] BECK J J,KIM J H,CAMPBELL1 B C,et al.Fungicidal activities of dihydroferulic acid alkyl ester analogues[J]. Journal of Natural Products,2007,70(5):779-782.DOI:10.1021/np0606345.
[20] KUMAR R,RAMACHANDRAN U,SRINIVASAN K,et al.Design,synthesis and evaluation of carbazole derivatives as PPARα/γdual agonists and antioxidants[J].Bioorganic&Medicinal Chemistry,2005,13(13):4279-4290.DOI:10.1016/j.bmc.2005.04.018.
[21] MARCHIANI A, MAMMI S, SILIGARDI G,et al.Small molecules interacting with a-synuclein:antiaggregating and cytoprotective properties[J]. Amino Acids, 2013, 45(2):327-338. DOI:10.1007/S00726-013-1503-3.
[221]王卫华,曽晓鹰,年寅,等.姜酮的NMR解析[J].云南大学学报,2013,35(4):530-535.DOI:10.7540/j.ynu.20120626.
[23] PANDEY G, KARTHIKEYAN M, MURUGAN A. New Intramolecular a-arylation strategy of ketones by the reaction of silyl enol ethers to photosensitized electron transfer generated arene radical cations:construction of benzannulated and benzospiroannulated compounds[J].Journal of Organic Chemistry, 1998,63(9):2867-2872.DOI:10.1021/jo9718612.
[24] JIANG J J, DU J L, LIAO D H, et al. Efficient Co(OAc)2-catalyzed aerobic oxidation of EWG-substituted 4-cresols to access4-hydroxybenzaldehydes[J].Tetrahedron Letters, 2014, 55(8):1406-1411.DOI:10.1002/chin.201429084.
[25] MILLER N J,RICE-EVANS C,DAVIES M J,et al.A novel method for measuring antioxidant status in premature neonates[J]. Clinical Science,1993,84(4):407-412.DOI:10.1042/cs0840407.
[26] BUTKO VIC V, KLASINC L,BORS W. Kinetic study of flavonoid reactions with stable radicals[J]. Journal of Agricultural and Food Chemistry,2004,52(10):2816-2820.DOI:10.1021/jfD49880h.
[27] LUCHSINGER W W, COMESKY R A. Reducing power by the dinitrosalicylic acid method[J].Analytical Biochemistry, 1962,4(4):346-347.DOI:10.1016/0003-2697(62)90098-2.
[28] BENZIE I F,STRAIN J J.The ferric reducing ability of plasma(FRAP)as a measure of"antioxidant power":the FRAP assay[J].Analytical Biochemistry, 1996,239(1):70-76.DOI:10.1006/abio.1996.0292.
[29]肖朝江,邱琳,徐伟,等.长果颈黄芪化学成分和抗氧化活性研究[J].中草药,2015,46(1):22-27.DOI:10.7501/j.issn.0253-2670.2015.01.006.
[30]张华,周志钦,席万鹏.15种柑橘果实主要酚类物质的体外抗氧化活性比较[J].食品科学,2015,36(11):64-70.DOI:10.7506/spkx1002-6630-201511013.
[2]王忠雷,杨丽燕,张小华,等.天然产物抗氧化活性成分研究进展[J].药物评价研究,2012,35(5):386-390.DOI:10.7501/j.issn.0253-6376.
[3] NASH K M.,AHMED S. Nanomedicine in the ROS-mediated pathophysiology:applications and clinical advances[J].Nanomedicine,2015, 11(8):2033-2040.DOI:10.1016/j.nano.2015.07.003.
[4] ROESSNERA A, KUESTERA D, MALFERTHEINERB P, et al.Oxidative stress in ulcerative colitis-associated carcinogenesis[J].Pathology Research and Practice, 2008, 204(7):511-524.DOI:10.1016/j.prp.2008.04.011.
[5] WOOTTON-BEARD P C,RYAN L.Improving public health?:the role of antioxidant-rich fruit and vegetable beverages[J]. Food Research International,44(10):3135-3148.DOI:10.1016/j.foodres.2011.09.015.
[6] VENKAT R D,ANKOLA D D,BHARDWAJ V.Role of antioxidants in prophylaxis and therapy:a pharmaceutical perspective[J].2006,13(3):189-207.DOI:10.1016/j.jconrel.2006.04.015.
[7]李文林,黄凤洪.天然抗氧化剂研究现状[J].粮食与油脂,2003,10(10):10-13.
[8]刘燕,杨智玲,魏法山,等.天然抗氧化剂的研究现状[J].粮油加工:电子版,2014(4):66-70.
[9]张献忠,黄海智,钟烈洲,等.植物提取物体外抗氧化活性评价方法研究进展[J].中国粮油学报,2012,27(11):122-128.
[10]李杰,赵声兰,陈朝银.食用油天然抗氧化剂的研究与开发[J].食品工业科技,2015, 36(2):373-378. DOI:10.13386/j.issn1002-0306.2015.02.073.
[11]陈晓迪,刘飞,徐虹.脂溶性天然抗氧化剂的研究进展[J].食品科学,2017,38(3):299-304.DOI:10.7506/spkx1002-6630-201703047.
[12]鲁玉妙,马惠玲.植物多酚SCI文献计量及生物活性研究热点分析[J].食品科学,2013, 34(23):375-383. DOI:10.7506/spkx1002-6630-201323074.
[13]赵秀玲.姜黄的化学成分、药理作用及其资源开发的研究进展[J].中国调味品,2012, 37(5):9-13. DOI:10.3969/j.issn.1000-9973.2012.05.003.
[14]赵革平,洪行球,李万里,等.姜黄醇提取物对抗体外LDL氧化修饰作用的研究[J].浙江中医学院学报,1999, 23(2):27-28.DOI:10.16466/j.issn1005-5509.1999.02.015.
[15]曾维才,石碧.天然产物抗氧化活性的常见评价方法[J].化工进展,2013,32(6):1205-1213.DOI:10.3969/j.issn.1000-6613.2013.06.001.
[16]马龙利,李岗,叶菲菲,等.6-姜酚的分离纯化及抗氧化能力研究[J].食品科技,2016, 41(8):206-209. DOI:10.13684/j.cnki.spkj.2016.08.048.
[17]陈洪璋,李伟,肖苏尧,等.桉叶提取物中抗氧化活性物分离纯化、结构鉴定及其活性的研究[J].现代食品科技,2018, 34(4):94-102.DOI:10.13982/j.mfst.1673-9078.2018.04.016.
[18] TAKASHI K,SACHIKO I,KAORU N,et al.Asymmetric synthesis of enantiomerically pure zingerols by lipase-catalyzed transesterification and efficient synthesis of their analogues[J]. Tetrahedron Asymmetry,2013,24(11):621-627.DOI:10.1016/j.tetasy.2013.04.013.
[19] BECK J J,KIM J H,CAMPBELL1 B C,et al.Fungicidal activities of dihydroferulic acid alkyl ester analogues[J]. Journal of Natural Products,2007,70(5):779-782.DOI:10.1021/np0606345.
[20] KUMAR R,RAMACHANDRAN U,SRINIVASAN K,et al.Design,synthesis and evaluation of carbazole derivatives as PPARα/γdual agonists and antioxidants[J].Bioorganic&Medicinal Chemistry,2005,13(13):4279-4290.DOI:10.1016/j.bmc.2005.04.018.
[21] MARCHIANI A, MAMMI S, SILIGARDI G,et al.Small molecules interacting with a-synuclein:antiaggregating and cytoprotective properties[J]. Amino Acids, 2013, 45(2):327-338. DOI:10.1007/S00726-013-1503-3.
[221]王卫华,曽晓鹰,年寅,等.姜酮的NMR解析[J].云南大学学报,2013,35(4):530-535.DOI:10.7540/j.ynu.20120626.
[23] PANDEY G, KARTHIKEYAN M, MURUGAN A. New Intramolecular a-arylation strategy of ketones by the reaction of silyl enol ethers to photosensitized electron transfer generated arene radical cations:construction of benzannulated and benzospiroannulated compounds[J].Journal of Organic Chemistry, 1998,63(9):2867-2872.DOI:10.1021/jo9718612.
[24] JIANG J J, DU J L, LIAO D H, et al. Efficient Co(OAc)2-catalyzed aerobic oxidation of EWG-substituted 4-cresols to access4-hydroxybenzaldehydes[J].Tetrahedron Letters, 2014, 55(8):1406-1411.DOI:10.1002/chin.201429084.
[25] MILLER N J,RICE-EVANS C,DAVIES M J,et al.A novel method for measuring antioxidant status in premature neonates[J]. Clinical Science,1993,84(4):407-412.DOI:10.1042/cs0840407.
[26] BUTKO VIC V, KLASINC L,BORS W. Kinetic study of flavonoid reactions with stable radicals[J]. Journal of Agricultural and Food Chemistry,2004,52(10):2816-2820.DOI:10.1021/jfD49880h.
[27] LUCHSINGER W W, COMESKY R A. Reducing power by the dinitrosalicylic acid method[J].Analytical Biochemistry, 1962,4(4):346-347.DOI:10.1016/0003-2697(62)90098-2.
[28] BENZIE I F,STRAIN J J.The ferric reducing ability of plasma(FRAP)as a measure of"antioxidant power":the FRAP assay[J].Analytical Biochemistry, 1996,239(1):70-76.DOI:10.1006/abio.1996.0292.
[29]肖朝江,邱琳,徐伟,等.长果颈黄芪化学成分和抗氧化活性研究[J].中草药,2015,46(1):22-27.DOI:10.7501/j.issn.0253-2670.2015.01.006.
[30]张华,周志钦,席万鹏.15种柑橘果实主要酚类物质的体外抗氧化活性比较[J].食品科学,2015,36(11):64-70.DOI:10.7506/spkx1002-6630-201511013.
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