小萝卜大戟(E.rapulum Kar.et Kir.)生物活性成分的提取与分离研究
详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文
摘要
本论文主要对大戟科药用植物小萝卜大戟(E.rapulum Kar.et Kir.)提取分离实验条件的选择、化学成分进行了系统的研究,同时对大戟属植物的生理活性和临床应用进行了阐述。
     本文对提取温度、提取时间、提取次数、料液比等对提取有较大影响的因素进行了分析。通过三水平四因素正交实验分析,确定了最佳工艺参数:提取温度为75℃,提取时间为75h,料液比为1:9,提取次数为5次。同时分析确定了其他参数:药材烘干温度为50~60℃,粉碎粒度60~80目,洗脱系统为石油醚-乙酸乙酯。本文使用闪式提取法和冷浸渍相结合代替了传统的提取方法,采用大溶剂瓶代替分液漏斗进行萃取,弥补了传统萃取方法中不能加热的缺点。
     小萝卜大戟经提取分离得到7个化合物。经化学方法和波谱学方法鉴定了其中的4个,分别为:甾醇,阿替斯烷型化合物:atis-16-en-13(s)-hydroxy-3,14-dion,两个五环三萜齐墩果烷型,即β-香树脂型(β-amyrane)化合物,其中阿替斯烷型化合物在大戟属植物中比较少见,本论文中分离得到的两个五环三萜齐墩果烷型单体在大戟属植物中为首次发现。
This dissertation focused on the chemical studies on E.rapulum Kar.et Kir., the Physiological Activity and Application of Euphorbia L. were discussed at the same time.
     This test analysised the influences on the extract effect during the extract and Chromatography with E.rapulum Kar.et Kir. ,such as :extract temperature、drying time、smashed level and solvent system.And the optimum parameters were choosed by Orthogonal Experiments Analysis of extract temperature、extract time、solid-liquid ratio、extraction times.They were temperature of 75℃, the ratio of solid to liquid of 1∶9, extract time of 75h and extraction times of 5 times.Aslo other parameters were determined : drying time 50~60℃, smashed level 60~80mu, solvent system petro ether-EtOAc.The extrat with shanshitiquqi reduced extract time and increased the extract efficiency compared with traditional method. Using new extraction method to make up for the deficiency of the traditional method.
     Seven compounds were extracted and purified by silica gel column chromatography. The structures of the five compounds were determined by physico- chemical properties and spectral analyses.They were :sitosterol、atis-16-en-13(s)- hydroxy-3,14-dion、9,11-ene-β-amyrane acetate、β-amyrane acetate -11-ketone.
引文
[1]中国科学院中国植物志编辑委员会.中国植物志.第四十四卷.第三分册.北京:科学出版社,1997.
    [2]焦莹,柳江华。刘桂芳,袁昌鲁.大戟属植物主要化学成分及其生理活性的研究进展,中草药,1990,21(2):39-44
    [3]师彦平,贺志军,贾忠建.大戟二萜活性及其生理活性的研究进展(Ⅰ).天然产物研究与开发,1998,11(5):85-89
    [4]江苏新医学院编.中药大辞典.上海:上海科学技术出版社.1986
    [5]中国药材公司编著.中国中药资源志要.北京:科学技术出版社.1994
    [6]江苏省植物研究所.新华本草纲要.第二册.上海:上海科学技术出版社.1991
    [7]Evans F.J.,Taylor S. E..Pro-infammatory,tumour promoting and anti-tumour diterpenes of the plant families Euphorbiaceae and Thymelaeaceae,In:Progress in the Chemistry of Organic Natural Products(Herz W. Et al ed). Vol.44. Sringer-Verlag.1983
    [8]Fakunle Christopher D.,Connolly Joseph D.,Rycroft David S..A new este r from the latex of Euphorbia lateriflora,Fitoterapia,1994,65(1):75-78
    [9]Appendino Giovanni,Jakupovic Sven,Tron Gian Cesare,Jakupovic Jasmin, Milon Veronique, Ballero Manro.Macrocyclic dterpenoids from Euphorbia semiperfoliata,Journal of Natural Products,1998,61(6):749-756
    [10]Ma Qinggao,Liu Wenzi,Wu Xiaoyun,Zhou Tianxi,Qin Guowen. Diterpenoids from Euphorbia frscheriana, Phytochemistry, 1997,44(4):663-666
    [11]Liu Wenzi, Wu Xiaoyun,Yang Genjin,Ma Qinggao,Zhou Tianxi,Tang Xican,Qin Guowen.12-Deoxyphorbol esters from Euphorbia frscheriana, Chinese Chemical Leters,1996,7(10):917-918
    [12]Fatope Majekodunmi O.,Zeng Lu,Ohayaga Joseph E.,Shi Guoen, Mclaughlin Jerry L..Selectively cytotoxic diterpenes from Euphorbia poisonii,Journal of Medicinal Chemistry,1996,39(4):1005-1008
    [13]Appendino Giovanni,Belloro Emanuela, Tron Gian Cesare, Jakupovic Jasmin,Ballero Mauro.Diterpenoids from Euphorbia pithyusa subsp.cupanii,Journal of Natural Products,1999,62(10):1399-1404
    [14]Shi Yanping,Jia Zhongjian,Jamil Lahham, Sadio Saleh. Pentacyclic diterpene esters from Euphorbia aleppica, Phytochemistry 1995,40 (4):1219-1221
    [15]Gunther Gabor,Martinek Tamas,Dombi Gyorgy,Hohmann Judit,Vasas Andrea.Sturctural characterization and dynamic NMR studies of a new peracylated macrocyclic diterpene, Magnetic Resonance in Chemistry, 1999,37:365-370
    [16]Hohmann J.,Vasas A.,Gnnther G.,Dombi Gy,Blazso G.,Falkay Gy, Mathe I,Jerkovich Gy.Jatrophane diterpenoids from Euphorbia peplus, Phytochemistry, 1999,51:673-677
    [17]Hideji Itokawa,Yoshitatsu Ichihara,Minako Yahagi, Kinzo Watanabe, Koichi Takeya. Lathyrane diterpenes from Euphorbia lathyris, Phytochemistry, 1990,29(6):2025-2026
    [18]Hohmann Judit,Evanics Ferenc,Vasas Andrea,Dombi Gyorgy, Jerkovich Gyula, Mathe lmre. A novel lathyrone diterpenoid from the roots of Euphorbia lathyris, Journal of Natural Products,1999,62:176-178
    [19]石建功,贾忠建,杨立.甘青大戟二萜化合物研究.高等学校化学学报,1994, 15(6):861-863
    [20]Hohmann Judit,Evanics Ferenc,Berta Laszlo,Bartok Tibor. from Euphorbia peplus, Planta Medica, 2000,66:291-294
    [21]Marco J.Alberto,Sanz-Cervera Juan F.,Yuste Alberto,Jakupovic Jasmin. lsoterracinolides A and B novel bishomoditerpene lactones from Euphorbia terracina, Journal of Natural Products, 1999,62:110-113
    [22]Marco J.Alberto,Sanz-Cervera Juan F,Yuste Alberto,Jakupovic Jasmin,Lex Johann. Terracinolides A and B,two bishomoditerpene lactones with a novel carbon framework from Euphorbia terracina, Journal of Organic Chemistry, 1996,61:1707-1709
    [23]Marco J.Alberto, Sanz-Cervera Juan F.,Yuste Alberto,Jakupovic Jasmin.Terracinolides from Euphorbia terracina,Phytochemistry, 1997,45(1):137-140
    [24]Jakupovic J.,Morgenstem T.,Binner M.,Silva M..Diterpenes from Euphorbia peplus, Pytochemistry, 1998,47(8):1601-1609
    [25]Xu Zhihong,Sun Jie,Xu Rensheng,Qin Guowei.Casbane diterpenoids from Euphorbia ebracteolata, Phytochemistry, 1998,49(1):149-151
    [26]Chen Hao,Jia Zhongjian.Diterpenes and sesquiterpene from two species-Structure elucidation of Euphorhylonal A and Euphoranin E, Indian Journal of Chemistry,1996, 3513: 1308-1310
    [27]Wu Tianshung,Lin Yuhmeei,Haruna Mitsumasa,Pan Deji,Shingu Tetsuro. Antitumor agents, 119.Kansuiphorins A and B,two novel antileukemic diterpene esters from Euphorbia kansu, Journal of Natural Products, 1991,54(3):823-829
    [28]Pan Deji,Hu Changgi,Chang Jerjang,Lee Thomas Tungying,Chen Yunpan, Hsu Hongyen, Mcphail Donald R.,Mcphail Andrew T.,Lee Kuohsiung. Kansuiphorin C and D,cytotoxic diterpenes from Euphorbia kansui, Phytochemistry,1991,30(3):1018-1020
    [29]Wu Dagang,Sorg B.,Adolf W.,Seip E. H.,Hecker E..Olig and macrocyclic diterpenes in Thymelaeaceae and Euphorbiaceae occurring and utilized in Yunnan(Southwest China) 2.Ingenane type diterpene esters from Euphorbia nematocypha Hand.-Mazz,Phytotherapy Research, 1992,6: 237-240
    [30]师彦平,杨立,贾忠建.大戟属植物中二萜酯和倍半萜甙结构的2D-NMR研究波谱学杂志, 1997,14(3):217-221
    [31]王文祥,丁杏苞.月腺大戟中二萜化学成分的研究,药学学报,1998,33(2):128-131
    [32]贾忠建,石建功,杨立.舟曲大戟对映-贝壳松烯二萜研究,高等学校化学学报, 1993, 14(5):651-652
    [33]Shi Jiangong,Jia Zhongjian Cui Yuxing.Novel tricyclic diterpenoids from Euphorbia micractina,Journal of Natural Products, 1995,58(1): 51-56
    [34]Shi Jiangong,Jia Zhongjian,Yang Li. Diterpenoids from Euphorbia micractina, Phytochemistry, 1993,32(1):208-210
    [35]Shi Jiangong,Jia Zhongjian.Diterpenoids from Euphorbia micractina, Phytochemistry 1995,38(6):1445-1447
    [36]焦莹,袁昌鲁,杨松松.东北大戟化学成分的研究.中草药, 1990,21(2):6-10
    [37]曹东,苏亚伦,杨峻山.大狼毒三萜类化学成分的研究,药学学报,1992,27(6):445-451
    [38]张峻,杨成金,吴大刚.小狼毒的三萜化学成分研究(Ⅱ),中草药,1998,29(7):433-435
    [39]姚新生.天然药物化学.第二版.北京:人民卫生出版社.1994
    [40]Amakura Yoshiaki,Yoshida Takashi.Tannins and related polyphenols of Euphorbiaceous plants XIV Euphorbin I,a new dimeric hydrolyzable tannin from Euphorbia watanabei, Chemical Pharmaceutical Bulletin, 1996, 44(7): 1293-1297
    [41]Ahn ByungTae,Oh Kap Jin,RoJai Seup,Lee Kyong Soon.A new flavonoid from Euphorbia ebracteolata, Planta Medica, 1996,62:383-384
    [42]Zaghloul Ahmed M..New flavonoid glycosides from Euphorbia dracunculoides,Mansoura Journal of Pharmaceutical Science,1993,9(2): 204-212
    [43]Murillo R..Jakupovic J..Glycosides from Euphorbia aucherii,1ng. Cienc.Quim.,1998, 18(2): 57-60
    [44]Shi Jiangong, Shi Yanping, Jia Zhongjian. Sesquiterpenoids from Euphorbia wangii, Phytochemistry, 1997,45(2):343-347
    [45]Ding Yili,Jia Zhongjian.Two phenolic derivatives from Euphorbia kansui,Phytochemistry, 1992,31(4):1435-1436
    [46]董云发,丁云梅.月腺大戟根中乙酰苯三酚衍生物,植物资源与环境1992,1(2):1-3
    [47]张涵庆,丁云梅.月腺大戟根中有效成分乙素和丙素的结构研究植物资源与环境,1992,1(3):6-9
    [48]王文祥,丁杏苞.月腺大戟根中乙酰间苯三酚类衍生物,药学学报1999, 34(7):514-517
    [49]王文祥,丁杏苞.月腺大戟的化学成分研究,中草药,1999,30(1):1-3
    [50]Wu Dagang, Sorg B., Hecker E.. Oligo- and Macrocyclic diterpenes in Thymelaeaceae and Euphorbiaceae occurring and utilized in Yunnan(Southwest China) 6 7igliane type diterpene esters from latex of Euphorbia prolifera, Phytotherapy Research, 1994,8:95-99
    [51]Cruz C. M., Kasper P,Cataldo A., Zamith H.P. S., Paumgartten F.J.R.. Tumor promoter-like activity of the molluscicidal latex of 'Crown-of-Thorns'(Euphorbia milii var. hislopfl) in the V79 metabolic cooperation assay, Brazil Journal of Medical Biological Research, 1996,29 (11):1519-1523
    [52]Gerd Vogg, Elke Mates, Jan Rothenburger, Norbert Hertkom, Stefan Achatz, Heinrich Sandermann Jr.. Tumor promoting diterpenes from Euphorbia leuconeura L., Phytochemistry,1999,51:289-195
    [53]李忌,郑耘,郑荣梁,贾忠建.天然二萜类化合物的抗肿瘤活性,肿瘤防治研究,1995,22(5):271-272
    [54]陈玲.飞扬草叶中的多酚类成分研究.中国中药杂志,1991,16(1):38-39
    [55]Tanaka Reiko,Kasubuchi Kazuaki,Kita Shunji,Tokuda Harukuni, Nishino Hoyoku, Matsunaga Shunyo. Bioactive steroids from the whole herd of Euphorbia chamaesyce,Journal of Natural Products, 2000,63(1):99-103
    [56]Lee Seung Ho,Park Ji Soo,Kim So Young, Chung See Ryun,Choi Sang Un.Cytotoxic effects of hydrolyzable tannins from some Euphorbia plants on human tumor cell lines, Yakhak Hoechi, 1997,41(4):524-529
    [57]CA 126:65375r
    [58]CA 126:308669
    [59]Kim Young Ho, Lee Sung Woo, Kim Hang Sub, Lee Seung Ho, Song Man Ki,Sung Young Chul,Lee Jung Joon.Inhibitory activities oftannins against reverse transcriptase and HIV-1 replication, Yakhak Hoechi, 1995,39(5):560-564
    [60]Satyanaryana V,Krupadanam G.L.David,Srimannarayana G.. Tetracyclic triterpenes from the latex of Euphorbia nivulia, Fitoterapia, 1992,63(1):82-83
    [61]Martinez-Vazquez Mariano, Apan Teresa O. Ramirez, Lazcano Maria Eugenia, Bye Robert.Anti-inflammatory active compounds from the n-hexane extract of Euphorbia hirta, Rev. Soc.Quim. Mex., 1999,43(3,4):103-105
    [62]CA 123:218433y
    [63]Galvez J.,Zarzuelo A.,Crespo M. E.,Lorente M. D.,Ocete M. A., Jimenez J..Antidiarrhoeic activity of Euphorbia hirta extract and isolation of an active Flavonoid consitituent,Planta Medica, 1993,59:333-336
    [64]Hatano Tsutomu, Yasuhara Taeko, Yoshihara Rieko, Ikegami Yukihiko, Matsuda Muneto,Yazaki Kazufumi, Agata Isao, Nishibe Sansei, Noro Tadataka, Yoshizaki Masao,Okuda Takuo. Inhibitory effects of Galloylated flavonoids on Xanthine Oxidase, Planta Medica,1991,57:83-84
    [65] Ito(nee Someya)Mayumi,Shimura Hiroshi,Watanabe Naoharu,Tamai Masaharu,Hanada Kazunori,Takahashi Akiko,Tanaka Yoshitaka, Arai Iwao, Zhang Pei-Ling,Rao Chung,ChenWei-Ming,Yang Jun-Shan,Su Ya-Lun,Wang Yu-Lan.Hepatoprotective compounds from Canarium album and Euphorbia nematocypha,Chemical Pharmaceutical Bulletin,1990,38(8):2201-2203
    [66]国家药典委员会编.中国药典(第一部).化学工业出版社,2005
    [67]何丽一.平面色谱方法及应用第二版[M].化学工业出版社,2005.
    [68]赵奎君,杨隽,刘锁兰.中药材,1999,22(5):231-233
    [69]丁毅力,刘育亭.准格尔大戟脂溶性成分的研究[J].中草药,1992,23(11):570-572
    [70]丁毅力,贾忠建.准格尔大戟化学成分的研究(Ⅰ)-一种新三萜的结构[J].兰州大学有机化学研究所,1989,11(10):1129-1130
    [71]北京医学院,北京中医学院.中草药成分化学.北京:人民卫生出版社,1981. 8-12
    [72]李汝辉.传质学基础.北京:北京航空学院出版社1987. 139-141
    [73]Teng R W,Ni W,Hua Y, Two New Tirucallane-Type Triterpenoid Saponins from Sapindus mukorossi[J].植物学报,2003,45(3):369-372
    [74]裴月湖,韩冰,冯宝民.狼毒大戟化学成分的研究[J].中草药,2002,33(7):591-593
    [75]王瑛,师彦平,贾忠建.巨枝大戟化学成分的研究[J].兰州大学学报(自然科学版),1999,35(4):62-66
    [76]张雷红,张现涛,叶文才.宽叶大戟化学成分的研究[J].天然产物研究与开发,2006,18:58-60
    [77]漆淑华,郭建伟,吴大刚.叶轮木的化学成分研究[J].天然产物研究与开发,2004,16(3):210-212
    [79]韦万兴,潘远江,张虹.从珠子草中分离得到的化合物:软木三萜酮在溶液和晶体中的结构[J].天然产物研究与开发,2004,16(3):201-203
    [81]陈玉,杨光忠.乌桕化学成分研究进展[J].天然产物研究与开发,1998,11(5):114-120
    [82]沈观冕.新疆的大戟属植物及地理分布[J].干旱区研究,1998,4(15):1-7
    [83]丁毅力,刘育亭.阿替烷类型二萜衍生物的NMR研究[J].波谱学杂志,1992,9(3):277-281
    [84]王利亚,万惠杰.茯苓化学成分的研究[J].中草药,1998,29(3):145-148.
    [85]仲兆金,许先栋.茯苓三萜化学成分及其光谱特征研究进展[J].中国药物化学杂志,1997,7(1):71-78.
    [86]龚复俊,袁晓,王国亮.3-氧,11α-羟基、△12-齐墩果烯及其类似化合物的13CNMR分析[J].波谱学杂志,1998,15(3):273-277.
    [87]肖生强,陈嵘,詹莉.齐墩果烷类皂甙天然产物13NMR化学位移规律及其结构智能解析[J].华中师范大学学报(自然科学版),2000,34(3):313-317.
    [88]方幼兰,林曦,林爱琴.玫瑰茄总皂甙的单体分离与结构分析[J].厦门大学学报(自然科学版),2004,43(5):657-660.

© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号

地址:北京市海淀区学院路29号 邮编:100083

电话:办公室:(+86 10)66554848;文献借阅、咨询服务、科技查新:66554700