地胆草抗氧化活性成分分离鉴定
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摘要
目的:研究地胆草(Elephantopus scaber)全草95%乙醇提取物的化学成分,并测定其抗氧化活性。方法:采用硅胶柱色谱,LH-20型羟丙基葡聚糖凝胶(Sephadex LH-20),开放ODS柱色谱和半制备高效液相色谱及重结晶等技术手段进行分离纯化,通过核磁共振波谱和质谱技术,结合文献数据进行结构鉴定。结果:分离得到14个化合物,分别鉴定为(E)-3-(3,4-二羟基苯亚甲基)-5-(3,4-二羟基苯基)-2(3H)-呋喃酮(1),秦皮乙素(2),二氢芥子醇(3),异地芰普内酯(4),咖啡酸(5),木犀草素-7-O-β-D-葡萄糖醛酸苷(6),木犀草素-7-O-β-D-吡喃葡萄糖醛酸苷甲酯(7),绿原酸甲酯(8),blumenol A(9),(6R,9R)-3-氧代-α-紫罗兰醇-β-D-吡喃葡萄糖苷(10),byzantionoside B(11),3,5-O-二咖啡酰奎宁酸甲酯(12),3,4-O-二咖啡酰奎宁酸甲酯(13),4,5-O-二咖啡酰奎宁酸甲酯(14)。结论:其中化合物1～4和8～10为首次从地胆草属植物中分离得到,化合物11为首次从地胆草植物中分离得到。对从地胆草中分离的12个化合物进行了清除1,1-二苯基-2-三磷基苯肼(DPPH)自由基和2'-联氨-双-3-乙基苯并噻唑啉-6-磺酸(ABTS+)自由基实验,结果显示化合物1,2,5,6,12和13具有显著的抗氧化活性。
Objective: To study the chemical constituents of 95% ethanol extract of the whole plant of Elephantopus scaber and investigate its antioxidant activity. Method: The chemical constituents were isolated and purified by silica gel column chromatography, Sephadex LH-20 column chromatography, ODS column chromatography,semi-preparative high performance liquid chromatography( HPLC) and recrystallization methods,while their structures were identified on the basis of nuclear magnetic resonance( NMR),mass spectrometry and comparison of their spectral data with those reported in the literature. Result: Fourteen compounds were isolated and their structures were identified as:( E)-3-( 3,4-dihydroxybenzylidene)-5-( 3,4-dihydroxyphenyl)-2( 3 H)-furanone( 1),esculetin( 2),dihydrosyringenin( 3),( +)-isololiolide( 4),caffic acid( 5),luteolin-7-O-β-D-glucuronide( 6),luteolin-7-O-β-D-glucuronide methyl ester( 7),chlorogenic acid methyl ester( 8),blumenol A( 9),( 6 R,9 R)-3-oxo-α-ionol-β-D-glucopyranoside( 10),byzantionoside B( 11),3,5-O-dicaffeoyl quinic acid methyl ester( 12),3,4-O-dicaffeoyl quinic acid methyl ester( 13) and 4,5-Odicaffeoyl quinic acid methyl ester( 14). Conclusion: Compounds 1-4 and 8-10 were isolated from the genus Elephantopus for the first time. Compound 11 was isolated from E. scaber for the first time. The DPPH radical and ABTS+radical scavenging experiments on twelve of these compounds showed that compounds 1,2,5,6,12 and13 had significant antioxidant activity.
Objective: To study the chemical constituents of 95% ethanol extract of the whole plant of Elephantopus scaber and investigate its antioxidant activity. Method: The chemical constituents were isolated and purified by silica gel column chromatography, Sephadex LH-20 column chromatography, ODS column chromatography,semi-preparative high performance liquid chromatography( HPLC) and recrystallization methods,while their structures were identified on the basis of nuclear magnetic resonance( NMR),mass spectrometry and comparison of their spectral data with those reported in the literature. Result: Fourteen compounds were isolated and their structures were identified as:( E)-3-( 3,4-dihydroxybenzylidene)-5-( 3,4-dihydroxyphenyl)-2( 3 H)-furanone( 1),esculetin( 2),dihydrosyringenin( 3),( +)-isololiolide( 4),caffic acid( 5),luteolin-7-O-β-D-glucuronide( 6),luteolin-7-O-β-D-glucuronide methyl ester( 7),chlorogenic acid methyl ester( 8),blumenol A( 9),( 6 R,9 R)-3-oxo-α-ionol-β-D-glucopyranoside( 10),byzantionoside B( 11),3,5-O-dicaffeoyl quinic acid methyl ester( 12),3,4-O-dicaffeoyl quinic acid methyl ester( 13) and 4,5-Odicaffeoyl quinic acid methyl ester( 14). Conclusion: Compounds 1-4 and 8-10 were isolated from the genus Elephantopus for the first time. Compound 11 was isolated from E. scaber for the first time. The DPPH radical and ABTS+radical scavenging experiments on twelve of these compounds showed that compounds 1,2,5,6,12 and13 had significant antioxidant activity.
引文
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[21]张婷婷,曹跃,曹佳,等.火绒草的咖啡酰类成分研究[J].中药材,2017,40(1):90-93.
[22]周岳,曾婷,李丽梅.光叶丁公藤酚性成分研究[J].中草药,2016,47(9):1496-1500.
[23]郭林新,马羊民,乔珂,等.三叶木通化学成分及抗氧化活性[J].中成药,2017,39(2):338-342.
[24]刘飞,李佳,张永清.栝楼雄株茎叶黄酮类化合物的分离及其清除DPPH能力研究[J].中草药,2016,47(23):4141-4145.
[25]朱求方,王永毅,瞿海斌.连线草的化学成分研究[J].中草药,2013,44(4):387-390.
[2]郭妍,陈晨,高纯,等.地胆草的化学成分研究[J].天然产物研究与开发,2016,28(7):1051-1054.
[3]张海波,孔丽娟,梁侨丽,等.地胆草的化学成分[J].中国实验方剂学杂志,2011,17(3):101-103.
[4] But P P H,Hon P M,CAO H,et al. Sesquiterpene lactones from Elephantopus scaber[J]. Phytochemistry,1997,44(1):113-116.
[5]李阳,张春云,林挺,等.白花地胆草的化学成分研究[J].中国中药杂志,2013,38(11):1751-1756.
[6]梁侨丽,龚祝南,绪广林,等.地胆草倍半萜内酯化合物体外抗肿瘤作用的研究[J].天然产物研究与开发,2008,20(3):436-439.
[7]王淑慧,张屏,伊丽娜,等.蒙药材藜芦的化学成分和抗氧化活性研究[J].中药材,2018,41(3):618-622.
[8]张小娜,邹先伟,李莹,等.茯砖茶不同溶剂提取物抗氧化活性研究[J].中国医药导报,2014,11(10):9-13.
[9] Tanka S,Okabe T,Naka Jima S,et al. BE-23372M,a novel protein tyrosine kinase inhibitor.Ⅲ. Synthesis[J]. J Antibiot,1994,47(3):297-300.
[10]曹捷,秦艳,尹成乐,等.紫花地丁化学成分及抗氧化活性[J].中国实验方剂学杂志,2013,19(21):77-81.
[11]毛晨梅,李杉杉,许琼明,等.枸骨茎的化学成分研究[J].中草药,2016,47(6):891-896.
[12]阎新佳,郑威,温静,等.白花败酱草的化学成分研究[J].中草药,2017,48(2):247-251.
[13]贾献慧,王晓,张永清.忍冬藤酚酸类化学成分分离[J].中国实验方剂学杂志,2015,21(5):69-71.
[14] XUE P F,LIANG H,WANG B,et al. Chemical constituents from Potentilla multifida L.[J]. J Pharm Sci US,2005,14(2):86-88.
[15]邵帅,严铭铭,毕胜男,等.小飞蓬中黄酮类化学成分研究[J].中国中药杂志,2012,37(19):2902-2905.
[16] ZHU X D,DONG X J,WANG Y F,et al. Phenolic compounds from Viburnum cylindricum[J]. Helv Chim Acta,2005,88(2):339-342.
[17] XIA L Z,ZHOU M,XIAO Y H,et al. Chemical constituents from Helwingia japonica[J]. Chin J Nat Med,2010,8(1):16-20.
[18]赵建强,辛海量,蒋益萍,等.唐古特白刺叶的化学成分研究[J].中草药,2016,47(7):1090-1093.
[19]崔锡强,李杏翠,王磊,等.蚕沙化学成分研究[J].中国中药杂志,2008,33(21):2493-2496.
[20]孙昱,马晓斌,刘建勋.野菊花心血管活性部位化学成分的研究[J].中国中药杂志,2012,37(1):61-65.
[21]张婷婷,曹跃,曹佳,等.火绒草的咖啡酰类成分研究[J].中药材,2017,40(1):90-93.
[22]周岳,曾婷,李丽梅.光叶丁公藤酚性成分研究[J].中草药,2016,47(9):1496-1500.
[23]郭林新,马羊民,乔珂,等.三叶木通化学成分及抗氧化活性[J].中成药,2017,39(2):338-342.
[24]刘飞,李佳,张永清.栝楼雄株茎叶黄酮类化合物的分离及其清除DPPH能力研究[J].中草药,2016,47(23):4141-4145.
[25]朱求方,王永毅,瞿海斌.连线草的化学成分研究[J].中草药,2013,44(4):387-390.