苍耳子中苯丙素类化学成分的研究

Phenylpropanoids from Fruits of Xanthium sibiricum

目的研究菊科植物苍耳(Xanthium sibiricum Patrin ex Widder)的干燥成熟带总苞的果实(苍耳子)中苯丙素类化学成分。方法采用正相硅胶柱色谱、反相十八烷基硅烷键合硅胶(ODS)柱色谱、Sephadex LH-20凝胶柱色谱和半制备高效液相色谱(HPLC)等色谱方法进行分离纯化,并结合高分辨质谱(HR-ESI-MS)、核磁共振(NMR)对分离得到的化合物进行结构鉴定。采用脂多糖(LPS)诱导的巨噬细胞RAW 264.7为筛选模型评价分离得到化合物的抗炎活性。结果从苍耳子体积分数95%乙醇提取物的乙酸乙酯萃取物中分离并鉴定了24个苯丙素类化合物,分别为c-藜芦酰乙二醇(1)、3,4'-二羟基-3'-甲氧基苯丙酮(2)、阿魏醛(3)、丁香脂素(4)、蛇菰宁(5)、落叶松脂醇(6)、愈创木基甘油(7)、3-hydroxy-l-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone(8)、salicifoliol(9)、6-(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclo[3.3.0]octan-2-ol(10)、榕醛(11)、jatrointelignan D(12)、icariol A2(13)、异落叶松脂素(14)、ehletianol C(15)、(7R,7'R,7”S,7‴S,8S,8'S,8”S,8‴S)-4”,4‴-dihydroxy-3,3',3”,3‴,5,5'-hexamethoxy-7,9';7',9-diepoxy-4,8”;4',8‴-bisoxy-8,8'-dineolignan-7”,7‴,9”,9‴-tetraol(16)、(7R,7'R,7”R,7‴S,8S,8'S,8”S,8‴S)-4”,4‴-dihydroxy-3,3',3”,3‴,5,5'-hexamethoxy-7,9';7',9-diepoxy-4,8”;4',8‴-bisoxy-8,8'-dineolignan-7”,7‴,9”,9‴-tetraol(17)、2-(4-hydroxy-3-methoxyphenyl)-1-(4-hydroxyphenyl)-propan-1,3-diol(18)、2,3-bis-(4-hydroxy-3-methoxyphenyl)-3-methoxypropanol(19)、楝叶吴萸素B(20)、threo-guaiacylglycerol-8-vanillin ether(21)、erythro-guaiacylglycerol-8-vanillin ether(22)、黄花菜木脂素B(23)和27-对香豆酰氧基熊果酸(24)。结论化合物6~24为首次从苍耳中分离得到。对分离得到的24个化合物进行抗炎活性筛选,其中,化合物14、21和23具有抗炎活性,其IC50值分别为(28.14±1.89),(16.78±0.68)和(38.42±2.15)μmol·L^(-1)。

OBJECTIVE To investigate phenylpropanoids from the dried fruits of Xanthium sibiricum Patrin ex Widder(Xanthii Fructus).METHODS The compounds were isolated and purified by silica gel column chromatography,ODS chromatography,Sephadex LH-20 and semi-preparative HPLC.Base on HR-ESI-MS and NMR,their structures were identified.The anti-inflammatory activity of the isolated compounds was evaluated by lipopolysaccharide(LPS)-induced macrophage RAW 264.7 as a screening model.RESULTS A total of 24 compounds were isolated from the ethyl acetate fraction of 95%ethanol extract and identified as c-veratroylglycol(1),β-hydroxypropiovanillone(2),ferulaldehyde(3),dihydrodehydrodiconifery alcohol(4),balanophonin(5),lariciresinol(6),guaiacylglycerol(7),3-hydroxy-l-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone(8),salicifoliol(9),6-(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclo[3.3.0]octan-2-ol(10),ficusal(11),jatrointelignan D(12),icariol A2(13),isolariciresinol(14),ehletianol C(15),(7R,7'R,7”S,7‴S,8S,8'S,8”S,8‴S)-4”,4‴-dihydroxy-3,3',3”,3‴,5,5'-hexamethoxy-7,9';7',9-diepoxy-4,8”;4',8‴-bisoxy-8,8'-dineolignan-7”,7‴,9”,9‴-tetraol(16),(7R,7'R,7”R,7‴S,8S,8'S,8”S,8‴S)-4”,4‴-dihydroxy-3,3',3”,3‴,5,5'-hexamethoxy-7,9';7',9-diepoxy-4,8”;4',8‴-bisoxy-8,8'-dineolignan-7”,7‴,9”,9‴-tetraol(17),2-(4-hydroxy-3-methoxyphenyl)-1-(4-hydroxyphenyl)-propan-1,3-diol(18),2,3-bis-(4-hydroxy-3-methoxyphenyl)-3-methoxypropanol(19),evofolin B(20),threo-guaiacylglycerol-8-vanillin ether(21),erythro-guaiacylglycerol-8-vanillin ether(22),cleomiscosin B(23),27-p-E-coumaroyloxyursolic acid(24).CONCLUSION Compounds 6-24 are obtained from this plant for the first time.Compounds 14,21,and 23 show anti-inflammatory activity in LPS-induced RAW 264.7 macrophages with the IC50 values of(28.14±1.89),(16.78±0.68),and(38.42±2.15)μmol·L^(-1),respectively.