黄山药化学成分代谢及其诱导细胞凋亡的分子机制的研究
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摘要
黄山药(Dioscorea panthaica Prain et Burkill)为薯蓣科(Dioscoreaceae)薯蓣属
    (Dioscorea)植物,是我国特有的植物。其药用部位为根茎,具有祛风除湿、清热解
    毒的功效,民间用以治疗胃病、跌打痨伤、牛马炭疽病。
     本文主要进行了化学成分、天然产物代谢和细胞凋亡的分子机制三方面的研究。
     本文利用大孔吸附树脂柱色谱,硅胶柱色谱,葡聚糖凝胶柱色谱、高效液相色谱
    等分离手段,从植物黄山药中分离出28种化合物,利用理化性质和光谱学技术,鉴
    定了其中的22种;其中,9个为新化合物,它们皆具有新的甾体骨架或新的苷元结构;
    3个化合物为首次从该属植物中分离得到。利用肠内菌代谢的方法,研究了dioscin(8)
    和pseudoprotodioscin(11)的代谢,共分离得到11种代谢产物,鉴定了其中的7种;
    其中,2个为新化合物。
     从黄山药根茎中分离得到的9个新化合物分别命名为:黄山药皂苷A(26-O-β-D-
    glucopyranosyl-3β,26-diol-20,22-seco-25(R)-furosta-5-en-20,22-dione-3-O-α-L-
    rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-β-D-glucopyranoside,
    dioscoreside A)(12),黄山药皂苷B(26-O-β-D-glucopyranosyl-3β,23α,26-triol-20,
    22-seco-25(R)-furosta-5-en-20,22-dione-3-O-α-L-rhamnopyranosyl-(1→2)-[α-L-
    rhamnopyranosyl-(1→4)]-β-D-glucopyranoside,dioscoreside B)(13),黄山药皂苷C
    (26-O-β-D-glucopyranosyl-3β,26-diol-23(α)-methoxyl-25(R)-furosta-5,20(22)-diene-
    3-O-α-L-rhamnopyranosyl-(1→2)-[α-L-rhamnopyranosyl-(1→4)]-β-D-
    glucopyranoside,dioscoreside C)(14),黄山药皂苷D(26-O-β-D-glucopyranosyl-3β,
    26-diol-20,22-seco-25(R)-furosta-5-en-20,22-dione-3-O-α-L-rhamnopyranosyl-(1→2)
    -[α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranoside,dioscoreside D)(15),黄山药
    皂苷E(26-O-β-D-glucopyranosyl-3β,26-diol-20,22-seco-25(R)-furosta-5,22(23)-dien-
    20(R)-methoxyl-3-O-α-L-rhamnopyranosyl-(1→2)-[α-L-rhamnopyranosyl-(1→4)]-
    β-D-glucopyranoside,dioscoreside E)(16),黄山药皂苷F(26-O-β-D-glucopyranosyl-3
    β,20(S),22,23(α),26-pentaol-25(R)-furosta-5-en-3-O-α-L-rhamnopyranosyl-(1→2)
    -[α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranoside,dioscoreside F)(17),黄山药
    皂苷G(26-O-β-D-glucopyranosyl-3β,17α,22,26-tetraol-20,22-seco-25(R)-furosta-5-
    
    
     沈冈茵科大学俗士学位论文 茵 耍
     一
     e卜20-o帅-3-O-Q-L-thallmpyTWsyl-(l一2)-[ a-L-thallmpyTallosyl-(l一4)]-p-
     D-glllCOPyransldC,iOSCOOSidCq(18),黄山药皂昔Ho6-O-fi-D-glllCOPyr8J:IDS外3日,
     23,26-iol-25仰-furostas,20 (2)-iene-3-O-a-L-thalnnppoosyL (一2)-[Q-L-
     thanmpyTWS仆门-4)]-p-D-glucopmpside,ioscoreside W(1幻,黄山药皂昔 1
     eg皿山enolone 3-O-u L-thamnopyTanosyl-(二一2)-[5 Altwsyl-(l-3)]-
     P-DglucopyTWside,ioscoreside I) (2卜13个己知化合物分别鉴定为:薯颓皂苦元
     (dosgeni,1),6一谷笛醇 ( D一sitosterol,2),棕橱酸 Oallllltlc acid, 3),豆笛醇
     Oti-删l,4),胡萝卜昔O删COstCfl,5),pfope 11 (),pTOg咖 Ill(7),薯萄皂昔
     (diOSCi 8),纤细皂苦协illin,9),26-O-5-D-ginCOmpsyl-25阅-filrostchs,20(22-
     dien-3 D,26-iol-3-O-a-L-hannopmpsyl-(l一2)]-fi-D-giopmpsyl(10),伪原薯
     葱皂苦…seudopTOtodiscm,11),pTCp此enolo朋 3-O-i-chacomoside (2),原薯裁皂
     苦 hotodioscin. 22)。其中,化合物 26-O-P-D-ltpyTanosyl-25仰-forOStas,20 (2)-
     山e11e-3 D,26-山*-3-O-Q-L-hannopyTthesylKI一2)]-p-D-glmpmpsy(10),伪原薯
     蒙皂苦(pseUdopfotodiscm,11)和 p一enolone 3-O-P-chaCotioside (2)为首次.
     从该属植物中分离得到。
     从 pseudmpdioscin的代谢产物中分离得到的 2个新化合物分别为:3-O-恤s-s
     一L-aPyrans叫-(- 2 andl~ 4)-B-D-glamPyransyll-25仰-sPirost-5-en3 P,20
     (S)-iol p,3-O-pis-a -L-illalllllopyTWSy-(l一2 andl-) D -D-glwiopyTWsyl]-
     25仰-filrostths-en-3 p,26-iol(VI);五个己知化合物分别为:p Ill(豆),延
     令草次苦(tilln?
The medicinal plant Dioscorea panthaica Pram et Burkill (Dioscoreaceae) is widely
     distributed in Yunnan, Sichuan, Guizhou and Hunan provinces of P. R. China. Its rhizomes
     have been known in traditional Chinese medicine as saponin-rich herbal medicine used for
     the treatment of gastropathy, anthrax, rheumatic heart disease and rheumarthritis. It has been
     reported that steroidal saponins were the main active components.
    
    
    
     In the course of a screening program to evaluate Dioscorea panthaica as a source of
     new interesting bioactive compounds, 28 compounds were isolated from the rhizome of
     Dioscorea pant haica with porous resin (DlO 1), silica gel, sephadex LLi-20, polyamide,
     HPLC etc. Among them, 22 compounds were elucidated on the basis of physi-.chemical and
     spectral methods. The nine new compounds were named as dioscoreside A (26-0- P
    
     glucopyranosyl-3 P , 26-diol-20, 22-seco-25 (R)-furosta-5-en-20, 22-dione-3-0- U
    
     rhamnopyranosyl- (1 梸2) -[ P -D-glucopyranosyl- (1 梸-3) j- P -D-glucopyranoside (12),
     dioscoreside B (26-0- P -D-glucopyranosyl-3 P , 23 a , 26梩riol-20, 22-seco-25 (R)-
     furosta-5-en-20, 22-dione-3-0- a -L-rhamnopyranosyl- (1棐2) ~[a -L- rhamnopyranosyl-
     (1 棏4) ]- P -D-glucopyranoside (13), dioscoreside C (26-0- P -D-glucopyranosyl-3 P,
     26-diol-23( a )-methoxyl-25 (R)-furosta-5, 20(22)-diene-3-0- a -L-rhamnopyranosyl- (1 梸
    
     2) -[ a -L-rhamnopyranosyl- (1 棏4) j- P -D-glucopyranoside (14), dioscoreside D (26-0-
     P -D-glucopyranosyl-3 P, 26-diol-20, 22-seco-25 (R)-furosta-5-en-20, 22-dione-3-0- a -
     L-rhaninopyranosyl- (1 棏2) -[ a -L- rhamnopyranosyl- (1 棏4) ]- P -D-glucopyranoside (15),
     dioscoreside E (26-0- P -D-glucopyranosyl-3 P, 26-diol-25 (R)-furosta-5, 22 (23)-dien-20
     (R)- methoxyl-3-0- a -L-rhamnopyranosyl- (1棐-2) ~[a -L- rbamnopyranosyl- (l棐4) II-
     P -D-glucopyranoside (16), dioscoreside F (26-0- P -D-glucopyranosyl-3 P , 20 (a ), 22, 23
     (S), 26-pentaol-25 (R)-furosta-5-en-3-0- a -L-rhamnopyranosyl- (1 棏 2 ) -[ a -L-
     rhamnopyranosyl- (1 棏-4) ]- P -D-glucopyranoside) (17), dioscoreside G (26-0- P -D-
     glucopyranosyl-3 P. 17 a, 22, 26-tetraol-20, 22-seco-25 (R)-furosta-5-en-20-one-3-0- a -
    
    
     -6-
    
    
    
    
    
    
    
    
    
     ABSTRACT
    
    
    
     L-rhaninopyranosyl- (1 棏~2) -[ a -L- rhamnopyranosyl- (1 棏~4) ]- P -D-glucopyranoside (18),
     dioscoreside H (26-0- P -D-glucopyranosyl-3 P, 23, 26-triol-25 (R)-furosta-5, 20 (22)-
     diene-3-0- a -L-rhamnopyranosyl- (1 棏-2) -[ a -L- rhamnopyranosyl- (1 棏-4) ]- P -D-
     glucopyranoside (19), dioscoreside I (pregnadienolone 3-0- a -L- rhamnopyranosyl- (1 梸
     2) -[ P -D-glucopyrnosyl- (1 棏-3)]- P -D-glucopyranoside) (20). They have novel carbon
     skeletons or new aglycones. The known compounds were identified as diosgenin (1), P -
     sitosterol (2), palinitic acid (3), stigmasterol (4), daucosterol (5), progenin 11(6), progenin III
     (7), dioscm (8), gracillin (9), 26-0- P -D-glucopyranosyl-25 (R)-furosta-5, 20 (22)-diene-3 P.
     26-diol-3 -0-[ a -L-rhamnopyranosyl-( 1 梸 2)]- P -D-glucopyranosyl (10), pseudoprotodiscin
     (11), pregnadienolone 3-0- P -chacotrioside (21), protodioscin (22)~ Among them, 26-0-
     P - D- glucopyranosyl- 25 (R)- furosta- 5, 20 (22) -diene- 3 P, 26- did- 3-0 -[ a -L-
     rhamnopyranosyl-(1 棏- 2)]- P -D-glucopyranosyl (10), pseudoprotodiscin (11) and
     pregnadienolone 3-0- P -chacotrioside (21) were isolated from this genus for the first time.
    
    
    
     The investigation on the metabol
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