苍耳子中苯丙素类化学成分的研究

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-dioxabicyclo3.3.0]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。

Phenylpropanoids from Fruits of Xanthium sibiricum

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-dioxabicyclo3.3.0] 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.