益智的化学成分及其神经保护作用

Chemical constituents from the fruits of Alpinia oxyphylla and their neuroprotective effects

采用正相硅胶、MCI、RP-18、Sephadex LH-20、制备薄层色谱及半制备HPLC等分离手段,并结合HR-ESIMS、NMR、ECD、X-单晶衍射等结构鉴定方法,从益智干燥果实90%乙醇提取物的乙酸乙酯部位中分离得到14个化合物,分别鉴定为:(2R,5R,7R,10S)-2,7-dihydroxyl-eudesmane-3(4),11(12)-diene(1)、α-rotunol(2)、diketone I(3)、(1S,4S,5R,7S)-1-hydroxyl-eremophilane-9(10),11(12)-diene-8-one(4)、cyperusol A1(5)、(6R,9S,10S)-10-hydroxyl-11,12,13-trinor-cadinane-4(5)-ene-3-one(6)、(2E,4E)-6-hydroxy-2,6-dimethylhepta-2,4-dienal(7)、益智醇(8)、益智酮A(9)、(5R)-5-羟基-1,7-二苯基-3-庚酮(10)、(5S)-5-羟基-7-(4″-羟基)-苯基-1-苯基-3-庚酮(11)、(5S)-5-羟基-7-(4″-羟基-3″-甲氧基)-苯基-1-苯基-3-庚酮(12)、7-(4″-羟基-3″-甲氧基)-苯基-1-苯基-3,5-庚二酮(13)、bis-(2-ethylhexyl)terephthalate(14)。化合物1~6为倍半萜类化合物,其中化合物1为新的桉烷型倍半萜类化合物,化合物7为单萜类化合物,化合物8~13为二苯基庚烷类化合物,化合物2~6、14为首次从益智中分离得到。H2O2氧化损伤SH-SY5Y细胞实验表明,化合物2、6、7、12和13在低、中浓度下具有神经保护作用,尤其是化合物6在低、中、高浓度下细胞存活率均高于阳性药表没食子儿茶素没食子酸酯(EGCG),显示较好的神经保护作用。

Fourteen compounds were isolated from the ethyl acetate fraction of 90%EtOH extracts of the dried fruits of Alpinia oxyphylla by silica gel,MCI,RP-18,Sephadex LH-20,TLC and semi-preparative HPLC column chromatography.Their structures were identified by HR-ESI-MS,UV,IR,NMR,ECD and X ray single crystal diffraction spectroscopic data as:(2R,5R,7R,10S)-2,7-dihydroxyl-eudesmane-3(4),11(12)-diene(1),α-rotunol(2),diketone I(3),(1S,4S,5R,7S)-1-hydroxyl-eremophilane-9(10),11(12)-diene-8-one(4),cyperusol A1(5),(6R,9S,10S)-10-hydroxyl-11,12,13-trinor-cadinane-4(5)-ene-3-one(6),(2E,4E)-6-hydroxy-2,6-dimethylhepta-2,4-dienal(7),oxyphyllacinol(8),yakuchinone A(9),(5R)-5-hydroxy-1,7-diphenylhept-3-heptanone(10),(5S)-5-hydroxy-7-(4″-hydroxyphenyl)-1-phenylhept-3-heptanone(11),(5S)-5-hydroxy-7-(4″-hydroxyl-3″-methoxyphenyl)-1-phenyl-3-heptanone(12),7-(4″-hydroxy-3″-methoxyphenyl)-1-phenyl-3,5-heptadione(13),bis-(2-ethylhexyl)terephthalate(14).Compounds 1−6 were sesquiterpenoids in which compound 1 is a new eudesmane sesquiterpenoid and compound 7 was a monoterpenoid.Compounds 8−13 were diarylheptanoids,and compounds 2−6 and 14 were isolated from A.oxyphylla for the first time.The experiments on H2O2 induced SH-SY5Y cells showed that compounds 2,6,7,12 and 13 had neuroprotective effects at low and medium concentrations.In particular,compound 6 showed obvious neuroprotective effect at low,medium and high concentrations whose cell viability was higher than that of the positive control.