柿属植物中的化学成分及药理作用研究进展柿树科(Ebenaceae)也称之为柿科,全世界有Euclea、柿属(Diospyros)、Lissocarpus 3属,共500余种,我国仅有柿属共57种。
我国柿属植物原产于长江流域,现以黄河流域,广东、广西和云南等地广为栽培。
柿属植物由于其抗氧化、抗癌、降糖、抗菌、降血脂等多种显著的药理作用而成为了近年来的研究热点。
现代研究表明,柿属植物含有黄酮类、萜类、萘醌萘酚类、香豆素类、甾醇类、脂肪酸、有机酸类、挥发性成分等多种化学成分,具有抗氧化、降糖、降血脂、防癌、止血等多种药理作用,且对心血管系统、血液系统级神经系统等具有良好的临床效果。
本文就柿属药材的化学成分、药理作用等方面的研究进行综述,梳理柿属药材的化学活性成分及已经明确的药理作用和机制,为柿属药材的进一步开发和研究提供依据。
1 柿树科植物的化学成分近30年来报道的柿属植物中化学成分复杂,主要含有黄酮类、萜类、萘醌萘酚类化合物,此外还含有香豆素类、甾醇类、脂肪酸、有机酸类、挥发性成分等多种化合物。
1.1 黄酮类化合物柿属植物中含有大量黄酮类化合物,对现有文献分析,从柿属中分到的化合物主要为黄酮醇及其苷类成分,基本上以槲皮素和山柰素为母核,如图1和表1所示:图 1 黄酮类化合物母核结构Fig.1 Nucleus structures of flavonoids表1 主要黄酮类化合物Table1 Main flavonoidsName MW MF ReferenceKaempferol 286.2364 C15H10O6 2,20Quercetin 302.2357 C15H10O7 2,4,20Annulatin 332.2616 C16H12O8 2Myricetin 318.2351 C15H10O8 26Rutin 610.5175 C27H30O16 2,5Quercitrin 448.3769 C21H20O11 27Myricetin-3-O-alpha;-L-rhamnopyranoside 464.3763 C21H20O12 7Kaempferol-3-O-(2-galloyl)-glucoside 600.4812 C28H24O15 3Kaempferol-3-O-alpha;-L-rhamnopyranoside 432.3775 C21H20O10 28Kaempferol-3-O-beta;-D-galactopyranoside 448.3769 C21H20O11 2,5,20Kaempferol -3-O-beta;-D-glucopyranoside 448.3769 C21H20O11 2,3,5,14,24,25Kaempferol -3-O-beta;-D-xylopyramoside 418.3509 C20H18O10 14Kaempferol-3-O-alpha;-L-arabinoside 419.3509 C20H18O11 14Quercetin-3-O-alpha;-L-arabinoside 419.3509 C20H18O11 15Hyperoside 464.3763 C21H20O12 2,4,5,20Isoquercitrin 464.3763 C21H20O12 2,3,5,7,14,24,25Isorhamnetin-3-O-beta;-D-glucopyranoside 476.4300 C23H24O11 2Kaempferol-3-O-(2-galloyl)-glucoside 600.4811 C28H24O15 3Quercetin-7-O-beta;-D-rhamnopyranoside 448.3769 C21H20O11 7Quercetin-3-O-beta;-D-glucopyranoside 462.4035 C22H22O11 4Vitexin 432.3775 C21H20O10 2Luteolin 286.2363 C15H10O6 132-O-rhamnosyl-vitexin 902.7990 C39H50H24 2Genistein 270.2369 C15H10O5 7Isorhamnetin 316.2622 C16H12O7 7,18,221.2萜类化合物查阅文献可知,柿属植物中含有大量三萜类化合物,其中以五环三萜居多,常见结构为齐墩果烷型(Oleanane)、乌苏烷型(Ursane)、羽扇豆烷型(Lupane),此外还含有如木栓烷(Friedelane)、蒲公英烷(Taraxerane)等结构的三萜类化合物,如图2,表2所示。
图2 三萜类化合物母核结构Fig.2 Nucleus structures of triterpenes表2 柿属植物中的主要三萜类化合物Table.2 Main triterpenesName MW MF ReferenceOleanolic acid 456.7003 C30H48O3 2,5,8,2024-Hydroxyoleanolic acid 943.1221 C48H78O18 9Acetyloleanolic acid 498.7370 C32H50O4 29Olean-12-ene-3-one 424.7015 C30H48O 31alpha;-amyrin 426.7174 C30H50O 2,34beta;-amyrin 426.7174 C30H50O 2,30,31Ursolic acid 456.7003 C30H48O3 2,7,17,20,34Ursolic acid acetate 498.7370 C32H50O4 34Ursolic acid stearate 650.8397 C36H58O10 32alpha;-Amyrenone 424.7015 C30H48O 35Uvaol 442.7168 C30H50O2 2,5,8,19,35Pomolic acid 472.7112 C30H48O4 11Barbinervic acid 488.6991 C30H48O5 2,9Rosamutin 650.8397 C36H58O10 2Baurenol 426.7174 C30H50O 31Marsformosanone 422.6856 C30H46O 3719alpha;-Hydroxy ursolic acid 472.7141 C30H48O4 2,5,3419beta;-Hydroxyursolic acid 472.7141 C30H48O4 3419alpha;,24-dihydroxy ursolic acid 488.7141 C30H48O5 2,5,9Betulin 442.7168 C30H50O2 6,12,17,34Betulinic acid 456.7003 C30H48O3 2,5,11,17,37Lupeol 426.7174 C30H50O 2,12,17,34Epi-lupeol 426.7174 C30H50O 35,36Lupenone 424.7015 C30H48O 39Betulinaldehydle 440.7009 C30H48O2 37Peregrinol 308.4986 C20H36O2 39Allobetulin 442.7168 C30H50O2 40Oxyallobetulin 456.7003 C30H48O3 40Diospyrolide 414.6205 C27H42O3 41Friedelin 426.7174 C30H50O 42Cerotic acid 399.7083 C26H52O2 21Taraxerol 426.7174 C30H50O 43Taraxerol acetate 468.761 C32H52O2 35Taraxeroone 424.7015 C30H48O 401.3萘醌或萘酚根据文献报道可知柿属植物中共分离出60多个萘醌及萘酚类化合物,其中萘醌类成分居多,且基本为含alpha;-萘醌基本母核的蓝雪醌(Plumbagin)或胡桃醌(Juglon)为结构单元的化合物。
如图3和表3所示:图3 萘醌类化合物结构单元Fig.3 Naphthoquinone compounds of the structural unit表3 属植物中的主要萘醌及萘酚类化合物Table.3 The main phenolic compounds naphthalene and naphthoquinoneName Group ReferencePlumbagin Plumbagin 43,553-Bromo-plumbagin Plumbagin 21,343-Chloro-plumbagin Plumbagin 43Droserone Plumbagin 43Methyl-naphthazarin Plumbagin 44-463-(2-Hydroxyethyl) plumbagin Plumbagin 43Diomelquinone Plumbagin 47,482-Methyl-5-methoxy-1,4- naphthoquinone Plumbagin 482-Methyl-3-hydroxy-5- methoxy-1,4-naphthoquinone Plumbagin 482-Methyl-5, 6-dimethoxy- 1,4-naphthoquinone Plumbagin 48Canaliculation Plumbagin 21,49Cyclocanaliculation Plumbagin 21,49,50Ebenone Plumbagin 517-Methyl-juglone Juglone 48,522-Ethoxy-7-methyl-juglone Juglone 533-Ethoxy-7-methyl-juglone Juglone 533-Methoxy-juglone Juglone 543-Methoxy-7-methyl-juglone Juglone 52,552-Methoxy-7-methyl-juglone Juglone 55Ismailin Juglone 49,50Chromenone ester Juglone 56Chromenone acid Juglone 56Yerriquinone Juglone 57Celebaquinone Juglone 47Isocelebaquinone Juglone 47Shinanolone Shinanolone 35,58Isoshinanolone Shinanolone 59Epi-isoshinanolone Shinanolone 218-Hydroxy-1,2-naphthoquinone 1,2-Naphthoquinone 60-623-Methyl-8-methoxy-1,2-naphthoquinone 1,2-Naphthoquinone 486-Methyl-8-methoxy-1,2-naphthoquinone 1,3-Naphthoquinone 47,63Elliptinone Plumbagin2 64-67Martinone Plumbagin2 45,52,65Ethylidene-6, 6-biplumbagin Plumbagin2 668-Hydroxy-isodiospyrin Plumbagin-uglone 52,65Ehretione Plumbagin-uglone 68Diospyrin Juglone2 21,44,52,69Isodiospyrin Juglone2 40,343-Methoxy-isodiospyrin Juglone2 542-Methoxy-isodiospyrin Juglone2 543, 3-Dimethoxy-isodiospyrin Juglone2 542, 3-Dimethoxy-isodiospyrin Juglone2 542, 2-Dimethoxy-isodiospyrin Juglone2 548-Hydroxy-3-methoxy-isodiospyrin Juglone2 54Cyclodiospyrin Juglone2 66Pentacyclic quinone Juglone2 70Diosindigo A Juglone2 65Diosindigo B Juglone2 70Diosquinone Juglone2 71Batacanone Juglone2 72Neodiospyrin Juglone2 21,35,52p-Dihydrodiospyrin Juglone2 733-Methoxydiospyrin Juglone2 73Tetrahydrodiospyrin Juglone2 738-Hydroxy-diospyrin Juglone2 562-Chlorodiospyrin Juglone2 563-Chlorodiospyrin Juglone2 563-Chloro-2-hydroxydiospyrin Juglone2 56Rotundiquinone Juglone2 35Biramentaceone Juglone2 56Mamegakinone Juglone2 21,52,67Xylospyrin Juglone2 73Bis-isodiospyrin Juglone2 34,401.4 挥发性成分安秋荣[1]等利用GC-MS的方法分离鉴定出柿叶中80个组分并用谱图检索的方式确认了75个化合物,其中55个为含氧化合物(占总挥发成分的95.22%),13个化合物的质量分数超过1%,55个含氧化合物中主要为(E)-2-己烯醛、(Z)-2-己烯醛和3,7,11,15-四甲基-2-十六烯-1-醇。
