海洋紅樹植物老鼠簕化學成分及活性研究進展

1、 海洋紅樹植物老鼠簕化學成分及活性研究進展劉泉1,2，林文翰2 季宇彬1(1. 哈爾濱商業(yè)大學生命科學與環(huán)境科學研究中心,哈爾濱150076; 2. 北京大學天然藥物及仿生藥物國家重點實驗室,北京100083)摘要：老鼠簕作為紅樹植物在民間有其廣泛的應用，但其有效成分和有效部位尚不明確。文章綜述了國內(nèi)外關(guān)于海洋紅樹植物老鼠簕的研究概況，其中包括化學成分研究，藥理作用等。關(guān)鍵詞：紅樹植物 ，老鼠簕，化學成分，藥理作用 Progress in the research on chemical constituents and activities of Acanthus Quan liu 1,2,

2、 Wenhan Lin2,Yubin Ji1(1.Center of Reserch and Development on L ife Science and Environmental Sciences, Harbin University of Commerce, Harbin 150076, China; 2. China State Key Laboratory of Natural and Biomimetic Drugs,Peking University,Beijing 100083)Abstract: Acanthus ilicifolius Linnaeus is widel

3、y use in folk as Mangrove,but the active components or the active parts was not clear.The progress of chemical constituents and pharmacologic activities of Acanthus ilicifolius Linnaeus were review in this article.Key word: Acanthus ilicifolius Linnaeus, Mangrove, chemical constituents, pharmacologi

4、c activities老鼠簕（Acanthus ilicifolius Linnaeus）是一種生長在熱帶海岸地帶的紅樹林植物，屬爵床科（Acanthaceae）老鼠簕屬（Acanthus）。其中屬于紅樹林植物的老鼠簕（Acanthus ilicifolius Linn）、小花老鼠簕（A. ebracteatus Vahl.）和廈門老鼠簕(A. xianmensis Zhang)在我國有分布,且老鼠簕和小花老鼠簕在民間混用1。海南民間用老鼠簕消腫、解毒、淋巴結(jié)腫大、急性肝脾疼痛、黃疸、胃痛和哮喘，將其根搗碎水煮，加上蜂蜜口服，是治療乙型肝炎的特效藥2。1、老鼠簕化學成分的研究11木質(zhì)素類化合

5、物：目前已從老鼠簕屬植物中分離得到木質(zhì)素類化合物類型包括：四氫呋喃類、芳基萘類。分離的木質(zhì)素的類型及結(jié)構(gòu)如下： Ia Ib 表1 木質(zhì)素類化合物名 稱類型結(jié)構(gòu)參考文獻(1)dihydroxymethyl-bis(3,5-dimethoxy-4-hydroxyphenyl)tetrahydrofuran-9 (or9)-O-glucopyranoside.(8R,7S,8R)-5,5-dimethoxylariciresinol-4-O-D-glucopyranoside alangilignoside C alangilignoside D (+)-syringaresinol-O-gluco

6、pyranoside (+)-syringaresinol-4-O-D-apiofuranosyl-(12)- O-D-glucopyranoside (+)-lyoniresinol 3-O-D-glucopyranoside (+)-lyoniresinol3a-2-(3,5-dimethoxy-4-hydroxy)-benzoyl-O-D-glucopyranoside (-)-lyoniresinol 3-O-D-glucopyranoside (+)-lyoniresinol 3a-O-D-galactopyranosyl-(16)-D-glucopyranoside (+)-lyo

7、niresinol 2a-O-D-galactopyranosyl-3a-O-D-glucopyranoside citrusin B magnolenin CabbbA/BR1=-D-Glc or H,R2=H or-D-GlcR1=H,R2=-D-Glc, R3=OMeR1=-D-Glc, R2=H, R3=OMeR1=-D-Glc, R2=R3=HR1=-D-GlcR1=Glc(21”)Api1,2,3,R1=H,R2=-D-Glc1,2,3,R1=H, R2=2-(3,5-dimethoxy-4-hydroxy)-benzoyl-O-Glc1,2,3,R1=H,R2=-D-Glc1,2

8、,3,R1=H,R2=Glc(6”1”)GalR1= Gal, R2=Glc64,665644,6,764,633541.2 苯乙醇苷類化合物： 表2 苯乙醇苷類化合物名 稱類型結(jié)構(gòu)參考文獻 acteoside campneoside -hydroxyacteoside ilicifolioside A leucosceptoside A martynosid isoacteoside phenethyl alcohol 8-O-D-glucopyranosyl-(12)-O-D-glucopyranoside cistanoide E ilicifolioside D phenethyl-O

9、-D-glucopyranoside campneoside ER1=R2=R3=OH ,R4=HR1=R2=R3=OH, R4=OMe R1=R2=R3=R4=OHR1=R2=R3=OH, R4=OEtR1=OMe, R2=R3=OH, R4=HR2=R3=OMe, R3=OH, R4=HR1=H,R2=-D-Glc, R3=R4=HR1=Rha,R2=H, R3=R4=OHR1=Rha,R2=H,R3=OH,R4=O-L-RhaR1=R2=R3=R4=HR1=-D-Glc, R2=H, R3=R4=OH4，6，7,844,694474,61061.3 生物堿類化合物：生物堿類化合物是老鼠簕

10、中特征的代謝產(chǎn)物，主要是苯駢噁唑嗪酮類化合物，以及2-苯駢噁唑啉酮 A B C D E表3 生物堿類化合物名 稱類型結(jié)構(gòu)參考文獻(2R)-2-O-glucopyranosyl-2H-1,4-benzoxazin-3(4H)-one (blepharin) (2R)-2-O-glucopyranosyl-4-hydroxy-2H-1,4-benzoxazin-3(4H)-one (2R)-2-O-glucopyranosyl-7-hydroxy-2H-1,4-benzoxazin-3(4H)-one 7-chloro-(2R)-2-O-glucopyranosyl-2H-1,4-benzoxaz

11、in-3(4H)-one (2R)-2-O-glucopyranosyl-5-hydroxy-2H-1,4-benzoxazin-3(4H)-one 7-chloro-(2R)-2-O-glucopyranosyl-4- hydroxy-2H-1,4-benzoxazin-3(4H)-one 2,4-dihydroxy-1,4-benzoxazin-3-one blepharigenin benzoxazolinone-2(3H)-one 4-hydroxy-benzoxazolinone-2(3H)-one 4-O-glucopyranosyl- benzoxazolinone-2(3H)-

12、one 5,5-bis-benzoxazoline-2,2-dione acanthicifoline trigonellin betaine 2-hudroxy-oxamilic acidABCDER1=R2=R3=H ,R4=GlcR1=R2=H,R3=OH, R4=GlcR1=OH, R2=R3=H ,R4=GlcR2=Cl,R3=R3=H, R4=GlcR1=H,R2=OH,R3=H,R4=GlcR2=Cl,R2=H, R3=OH,R4=GlcR1=R2=H,R3=OH R4=HR1=R2=R3=R4=HR=HR=OHR=Glc4,7,114,7,11,13 11117,11413,1

13、8512,13155141617551.4 四甲基環(huán)己烯類化合物： A B表6 四甲基環(huán)己烯類化合物名 稱類型結(jié)構(gòu)參考文獻 plucheoside B alangionoside C ebracteatoside A Premnaionosid (1S,3S,5R,6R,7E)-5,11-epoxy-megastigman-7-en-9 -one-3-O-D-glucopyranoside (6S,9S)-roseosideABR1=Glc，R2=R3=H R1=H,R2=Glc,R3=h R1=H, R2=H,R3=Glc(21”) ApiR= Glc(21”) Api4,6444551.5

14、 黃酮類化合物：表4 黃酮類化合物名 稱結(jié)構(gòu)參考文獻 quercetin quercetin 3-O-D-glucopyanoside apigenin 7-O-glucopyanoside methylapigenin 7-O-glucopyanuronate vicenin-2 schaftoside luteolin 7-O-D-glucuroside apigenin 7-O-D-glucuroside 5,4-dihydroxy-7,8-dimethoxy flavone hispidulin luteolin 7-O-glucoside apigenin 7-O-glucoside

15、 linaroside apigenin 7-O-D-rutinoside chrysoeriol-7-O-D-rutinoside hispidulin 7-O-rutinoside apigenin apigenin O-D-(6”-trans-p-coumaroyl)-glucoside apigenin 7-O-D(6-transp-coumaroyl)3-O-acetylglucopyranoside)R1=H,R2=OH,R3=H ,R4=R5=R6=OH, R7=HR1=H,R2=OH,R3=H ,R4=OH,R5=Glc,R6=OH, R7=HR1=H,R2=OGlcA,R3=

16、H,R4=OH,R5=R6=R7=H R1=H,R2=O-methyl-glucopyranuronate,R3=H,R4=OH,R5=R6=R7=HR1=Glc,R2=OH,R3=Glc,R4=OH,R5=R6=R7=HR1=Ara,R2=OH,R3=Glc,R4=OH,R5=R6=R7=HR1=H,R2=OGlcA,R3=H,R4=OH,R5=H,R6=OH,R7=HR1=H,R2=OGlcA,R3=H,R4=OH,R5=R6=R7=HR1=OMe,R2=OMe,R3=H,R4=OH,R5=R6=R7=HR1=H,R2=OH,R3=OMe,R4=OH,R5=R6=R7=HR1=H,R2=O

17、Glc,R3=H,R4=OH,R5=H,R6=OH,R7=HR1=H,R2=OGlc,R3=H,R4=OH,R5=R6=R7=HR1=H,R2=OGlc,R3=OMe,R4=OH,R5=R6=H,R7=MeR1=H,R2=OGlc(61”)Rha,R3=H,R4=OH,R5=R6=R7=HR1=H,R2=OGlc(61”)Rha, R3=H,R4=OH,R5=H,R6=OMe,R7=HR1=H,R2=OGlc(61”)Rha, R3=OMe,R4=OH,R5=H,R6=H,R7=HR1=H,R2=OH,R3=H ,R4=OH, R5=R6=R7=HR1=H,R2=OGlc(6”-trans-p

18、-coumaroyl),R3=H ,R4=OH, R5=R6=R7=HR1=H,R2=OGlc(6”-trans-p-coumaroyl-3”-O-actyl) R3=H ,R4=OH, R5=R6=R7=H16164，202044,74,5192121229235572020201.6三萜類化合物：目前從老鼠簕屬植物中分離得到三萜類化合物結(jié)構(gòu)有齊墩果烷型、烏蘇烷型、羽扇豆烷型和一種新穎的五環(huán)三萜機構(gòu)類型。 表5 三萜類化合物名 稱類型結(jié)構(gòu)參考文獻 -Amyrin Oleandic acid 3,24-dihydroxyolean-12-en-28-oic acid -Amyrin ursol

19、ic acid urs-12-en-28-oic acid 3-O-D-glucopyranosyl (12)-D-glucopyranoside urs-12-ene-3-L-rhamnopyranosyl (281)-D-glucopyranosyl ester lupeol -L-araninofuranosyl-(14)- -D-glucopy-ranosyl(13)- 3-hydroxy-lup-20(29)-ene acanthusol acanthusol 3-glucosideR1=H，R2=R3=Me R1=H,R2=Me,R3=COOH, R1=H, R2=CH2OH,R3

20、=COOH R1=H,R2=CH3R1=H,R2=COOHR1=Glc(21”)Glc,R2=COOHR1=-L-Rha,R2=COOGlc, R=H,R=GlcA(41”)AraR=HR=Glc242424242425252426272717 脂肪醇類化合物：從老鼠簕屬植物中分離得到脂肪醇苷類化合物。表7 脂肪醇類化合物名 稱結(jié)構(gòu)參考文獻（1）ebracteatoside B（2）ebracteatoside C（3）ebracteatoside D（4）ilicifolioside B（5）ilicifolioside CR1=-xyl, R2=-Glc, R3=HR1=H, R2=-Gl

21、c, R2=OHR1=-xyl, R2=H, R2=OHR1=-xyl, R2=-Glc, R3=OHR1=H, R2=Glc（6”1”）xyl R3=COOH4444,7,284,292、藥理活性研究進展21 抗氧化和肝保護作用：Babu BH等31做的藥理實驗表明，老鼠簕（Acanthus ilicifolius Linn）葉子的乙醇提取物能清由核黃素光還原法產(chǎn)生的過氧化物，該植物葉子提取物具有自由基清除活性。22 抗腫瘤活性 老鼠簕（Acanthus ilicifolius Linn）葉子的乙醇提取物顯示有抗腫瘤和抗癌活性，可減小腫瘤體積，使患腹水腫瘤動物的生命延長率達75%32。23

22、抗炎活性 老鼠簕（Acanthus ilicifolius Linn）具有止痛、抗炎作用33，另外，對2-苯駢噁唑啉酮的生物活性進行了廣泛的研究，顯示有止痛、解熱、抗驚厥、催眠、肌肉松弛、誘變、殺利什曼原蟲和抗真菌的作用34。3、結(jié)論 雖然老鼠簕被當作藥用，在民間有廣泛的應用，但其藥理活性的理論依據(jù)和產(chǎn)生活性的物質(zhì)基礎(chǔ)還尚不明確，鑒于老鼠簕具有多種藥理活性，為把其開發(fā)成新藥奠定理論基礎(chǔ)，故對老鼠簕進行全面的化學藥理方面的研究是十分必要的。參考文獻1 林鵬.中國紅樹林環(huán)境生態(tài)及經(jīng)濟利用M.高等教育出版社，1995：192 華南植物研究所. 南海植物志M. 第二卷.北京：科學出版社，1974：18

23、03 Ju Wu,Si Zhang,et al. Two new cyclolignan glycosides from Acanthus ilicifolius. Zeitschrift fuer Naturforschung,B:Chemical Science.2004,59(3):341-3444 Tripetch K，Ryoji K,Chayan P，et al. Megastigmane, aliphatic alcohol and benzoxazinoidglycosides from Acanthus ebracteatus. Phytochemistry，2001，58(6

24、):8115 Huo Chang-Hong,Wang Bin,Lin Wen-Han.Chemical constituents and pharmacological activites of Acanthus.Zhongguo Haiyang Yaowu,2004,23(3):39-446 Tripetch K,Mohamed SK,Ryoji K,et al.Lignan glucosides from Acanthus ilicifolius.Phytochemistry，2001,56(4):3697 Tripetch K,Pawadee N,et al. Chemical cons

25、tituents of A. volubilis.Biochemical systematics and ecology.2006,34(5):442-4458 Ismail LD,E-Tantwy M.Macro-and micromorphological as well as phytochemical studies of Acanthus mollis L.(Acanthaceae)J. Al-Azhar J Pharm Sci,1999,23:979 Wu, Jun; Zhang, Si; Long, Lijuan; Li, Qingxin. Structure and appli

26、cation of phenylethanoid glycoside-ilicifolioside A. Faming Zhuanli Shenqing Gongkai Shuomingshu (2003), 9 pp10 Jun Wu,Si Zhang et al.Phenylethanoid and aliphatic alcohol glycosides from Acanthusilicifolius.Phytochemistry,2003,63:49111 Tripetch K,Mohamed SK,Ryoji K,et al.Benzoxazinoid glucosides fro

27、m Acanthus ilicifolius.Phytochemistry,2001,58(4):63712 Udom K,Vallapa C.Chemical constituents of the roots of Acanthus ilicifolius. J Nat Prod, 1986,49(2):35513 Wolf RB,Spencer GF,Plattner,RD.Benzoxazoline,2,4-dihydroxy-1,4-benzoxazin-3-one,and143 glucoside from Acanthus mollis seed inhibit velvetle

28、af germination and growth. J. Nat.Prod,1985,48(1):5914 DSouza L,Wahidulla S,Mishra PD.Bisoxazolinone from the mangrove Acanthus ilicifolius15 .2006,37(7):971-97316 Tiwari, KP.,Minocha, PK.; Masood M. Acanthicifoline - a new alkaloid from Acanthus ilicifolius. Polish Journal of Chemistry 1980, 54(4):

29、857-817 Minocha PK.; Tiwari KP. Chemical constituents of Acanthus illicifolius Linn. Polish Journal of Chemistry 1980, 54(10): 2089-9018 Pratt K,Kumar P,et al.Cyclic hydroxamic acids in dicotyledonous plantsJ.Biochem Syst Ecol,1995,23(718):78119 Amer, Masouda E.; Abou-Shoer, Mohamed I.; Abdel-Kader,

30、 Maged S.; El-Shaibany, Amina M. S.; Abdel-Salam, Nabil A. Alkaloids and flavone acyl glycosides from Acanthus arboreus. Journal of the Brazilian Chemical Society (2004), 15(2), 262-266.20 Nair AG,Ramachandran PV. Methylapigenin 7-O-D-glucuronate-a new flavone glucoside from Acanthus ilicifoliusJ.J

31、Ind Chem Soc,1987,64(4):28821 Reynaud J,Couble A.Flavonoids from Acanthus mollis L.(Acanthaceae)J.Pharmazi,1988,43 (5):37322 Loukis A, Philianos S.Phytochemical investigation of Acanthus mollis LJ.Fitoterapia,1980, 51(4):18323 Glizin V, Ivancheva S,Karadzhov K,et al.Study of the plant Acanths longif

32、olius for physiologically active substances.Part IJ.Farmatsiya,1980,30(6):35.24 Amitabha G,Suniti M,Ashis K,et al.Pentacyclic triterpenoids and sterols from seven species of Mangrove J.Phytochemistry,1985,24(8):172525 Anam EM. Novel triterpenoid glycosides and triterpenoid acid from the root extract

33、 of Acanthus montanus (Acanthaceae)J.Indian J Chem Sect B:Org Chem Ind Med Chem,1997,36B(10):90126 Minocha PK,Tiwari KP. A triterpenoidal saponin from roots of Acanthus ilicifoliusJ.Phytochemistry,1981,20:13527 Anam EM.Pentacyclic triterpenoid from Acanthus montanus(Acanthaceae)J. Indian J Chem Sect