绞股蓝皂甙酸水解产物研究
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摘要
绞股蓝(Gynostemma pentaphyllum Thunb.Makion)为葫芦科(Cucurbitac-eae)多年生草质藤本植物。绞股蓝作为一味传统中药,常被用于治疗慢性气管炎和肝炎等疾病。绞股蓝皂甙为达玛烷型四环三萜骨架构,具有抗肿瘤、抗衰老、保护心脑血管等生物活性。另外,皂甙的水解亦可以作为一种获得结构多变的,种类丰富的类天然产物的手段。
通过硅胶、大孔树脂、葡聚糖凝胶LH-20,RP-18,MCI等柱层析方法,我们从绞股蓝总皂甙酸水解产物中分离得到了8个化合物,借助质谱(EI-MS, ESI-MS等),氢谱(1H-NMR),碳谱(13C-NMR)等波谱学方法鉴定了其中4个化合物,其结构均为达玛烷性骨架,分别是20R-21,24-cycle-3,25-dioldammar-23(24)-en-21-one,(20S,23R)-3β, 20β-dihy droxydamma-24-dien-21-oic acid-21,23-lactone,(20S)-3β,20,21,25-tetrahydroxy-21,24-cyclo dammarane,(20S)-3β,20-dihydroxy-24-dammarane-12,23-dione。
利用DPPH法我们测定了绞股蓝总皂甙,总皂甙在不同水解时间所得产物以及分离得到的单体皂甙元(或次生甙元)的抗氧化活性。测定结果为,总皂甙的IC50值为122.47 ug/mL;水解1,2,3,4小时后水解产物的IC50值分别为251.08 ug/mL,329.60 ug/mL,426.60 ug/mL,453.2 ug/mL。总皂甙的抗氧化活性最高;随着水解过程的进行(水解时间的延长),抗氧化活性逐渐减弱;单体甙元(或次生甙元)没有表现出抗氧化活性。
Being a Traditional Chinese Herbs, Gynostemma pentaphyllum Thunb. Makion is always used to treat chronic tracheitis and hepatitis in China. Gynosaponin, the main bioactive components of this herb, is active in anti-tumor, anti-aging and the protecting of cardiovascular and cerebrovascular.
Gynosaponin was acid-hydrolyzed in this assay, and the DPPH free radical scavenging capacity of the derivatives was evaluated. Eight compounds were isolated from the hydrolysis product by the means of silicon column, macroporous resin, sephadex-20, RP-18 and MCI chromatography. And finally, the structure of 4 dammarane type compounds were elucidated, through the spectroscopy analysis, namely, 20R-21,24-cycle-3,25-diol dammar-23(24)-en-21- one,(20S, 23R)-3β, 20β-dihydroxydamma-24-dien-21-oic acid 21,23-lactone,(20S)-3β,20, 21,25-tetrahydroxy-21,24-cyclodammarane , (20S)-3β,20-dihydroxy-24-dammarane-12,23- dione.
The DPPH free radical scavenging capacity of the gynosaponin, derivatives in different time during the hydrolysis procedure and the sapogenin was also evaluated. The results showed that the IC50 of gynosaponin was 122.47μg/mL, and the antioxidation activity decreased gradually with the time of hydrolysis, the IC50 of the derivatives was 251.08μg/mL,329.60μg/mL,426.60μg/mL,453.2μg/mL, respectively, according to the time (hydrolyzed for 1, 2, 3, and 4 hours). Precipitation of secondary gypenoside shown none antioxidation activity.
通过硅胶、大孔树脂、葡聚糖凝胶LH-20,RP-18,MCI等柱层析方法,我们从绞股蓝总皂甙酸水解产物中分离得到了8个化合物,借助质谱(EI-MS, ESI-MS等),氢谱(1H-NMR),碳谱(13C-NMR)等波谱学方法鉴定了其中4个化合物,其结构均为达玛烷性骨架,分别是20R-21,24-cycle-3,25-dioldammar-23(24)-en-21-one,(20S,23R)-3β, 20β-dihy droxydamma-24-dien-21-oic acid-21,23-lactone,(20S)-3β,20,21,25-tetrahydroxy-21,24-cyclo dammarane,(20S)-3β,20-dihydroxy-24-dammarane-12,23-dione。
利用DPPH法我们测定了绞股蓝总皂甙,总皂甙在不同水解时间所得产物以及分离得到的单体皂甙元(或次生甙元)的抗氧化活性。测定结果为,总皂甙的IC50值为122.47 ug/mL;水解1,2,3,4小时后水解产物的IC50值分别为251.08 ug/mL,329.60 ug/mL,426.60 ug/mL,453.2 ug/mL。总皂甙的抗氧化活性最高;随着水解过程的进行(水解时间的延长),抗氧化活性逐渐减弱;单体甙元(或次生甙元)没有表现出抗氧化活性。
Being a Traditional Chinese Herbs, Gynostemma pentaphyllum Thunb. Makion is always used to treat chronic tracheitis and hepatitis in China. Gynosaponin, the main bioactive components of this herb, is active in anti-tumor, anti-aging and the protecting of cardiovascular and cerebrovascular.
Gynosaponin was acid-hydrolyzed in this assay, and the DPPH free radical scavenging capacity of the derivatives was evaluated. Eight compounds were isolated from the hydrolysis product by the means of silicon column, macroporous resin, sephadex-20, RP-18 and MCI chromatography. And finally, the structure of 4 dammarane type compounds were elucidated, through the spectroscopy analysis, namely, 20R-21,24-cycle-3,25-diol dammar-23(24)-en-21- one,(20S, 23R)-3β, 20β-dihydroxydamma-24-dien-21-oic acid 21,23-lactone,(20S)-3β,20, 21,25-tetrahydroxy-21,24-cyclodammarane , (20S)-3β,20-dihydroxy-24-dammarane-12,23- dione.
The DPPH free radical scavenging capacity of the gynosaponin, derivatives in different time during the hydrolysis procedure and the sapogenin was also evaluated. The results showed that the IC50 of gynosaponin was 122.47μg/mL, and the antioxidation activity decreased gradually with the time of hydrolysis, the IC50 of the derivatives was 251.08μg/mL,329.60μg/mL,426.60μg/mL,453.2μg/mL, respectively, according to the time (hydrolyzed for 1, 2, 3, and 4 hours). Precipitation of secondary gypenoside shown none antioxidation activity.
引文
[1]潘峰,刘迪,黄翠霞等.绞股蓝皂甙的药理学临床研究[J].现代中西医结合杂志, 2006, 15(5): 674-676.
[2]谭华炳,赵世印,赵斌.绞股蓝的基础研究与组方应用研究概况[J].医学理论与实践, 2005, 18(5): 532-535.
[3]任颖,王秋玉,吴泽民等.绞股蓝皂甙的药理研究进展[J].中国实用中西医杂志,2001,14(1): 988-999.
[4] Wang W, Zhao Y, Rayburn ER, et. al. In vitro anti-cancer activity and structure–activity relationships of natural products isolated from fruits of Panax ginseng[J]. Cancer Chemother Pharmacol. 2007, 59: 589–601.
[5]杨彩霞,王大伟,诸平.竹本常松与绞股蓝[J].宝鸡文理学院学报(自然科学版). 1997, 17(4):53-56.
[6]唐晓玲,蒋桂平,夏培源.绞股蓝粗多糖的提取与初步分析[J].河南医科大学学报. 1996, 31(1): 87-90.
[7] You Lv, Xingbin Yang. Separation and quantification of component monosaccharides of the tea polysaccharides from Gynostemma pentaphyllum by HPLC with indirect UV detection. Food Chemistry. 2009, 112: 742–746.
[8] Chi Ai-Ping, Chen Jin-Ping. Morphological and structural characterization of a polysaccharide from Gynostemma pentaphyllum Makino and its anti-exercise fatigue activity. Carbohydrate Polymers. 2008, 74: 868–874.
[9]王昭晶,罗巅辉.碱提绞股蓝水溶性多糖的研究[J].食品研究与开发. 2006, 27 (5): 92-95.
[10]宋淑亮,吉爱国.绞股蓝多糖的分离纯化及其对神经细胞谷氨酸损伤的保护作用[J].天然产物研究与开发. 2008, 20: 229-232.
[11]罗巅辉,王昭晶.绞股蓝多糖的研究进展[J].生物技术通讯. 2005, 16(6): 703-707.
[12] Zhaojing Wang, Dianhui Luo. Antioxidant activities of di Verent fractions of polysaccharide puri Wed from Gynostemma pentaphyllum Makino. Carbohydrate Polymers. 2007, 68: 54–58.
[13]王海元,池爱平.绞股蓝多糖对运动小鼠组织抗氧化能力的影响.食品科学. 2008, 29(11): 616-619.
[14]沈爱宝,邵健.绞股蓝粗多糖抗癌作用的初步观察[J].南通医学院学报. 1995, 15(1): 148-153.
[15] Rujjanawate C, Kanjanapothi D, Amornlerdpison D. The anti-gastriculcer effect of Gynostemma pentaphyllun Makino[J]. Phytomedicine. 2004, 11:431-435.
[16]娄振岭,陈伟民,马丽萍.绞股蓝多糖对肿瘤细胞的抑制作用.河南医科大学学报[J]. 1996, 31(1): 87-88.
[17]肖增平,吉爱国,宋淑亮等.绞股蓝多糖对小鼠四氯化碳肝损伤的保护作用[J].中国生化药物杂志. 2008, 29(3): 186-188.
[18]宋淑亮,肖增平,吉爱国等.绞股蓝多糖对HepG2细胞酒精性损伤的保护作用[J].生化约物杂志2008, 29(5): 302-306.
[19]陈兢,王喆之.绞股蓝多糖的组成分析及其对质粒DNA的保护作用.中成药. 2009, 31(1): 92-95.
[20]魏守蓉,薛存宽,何学斌.绞股蓝多糖降血糖作用的实验研究.中国老年学杂志. 2005, 25(2):418-420.
[21]王临润,黄明珠.中国东南部4种绞股蓝中黄酮成分的分析[J].中草药. 2007, 38(4): 618-621.
[22]丁建南.疏花绞股蓝黄酮化合物的分离与鉴定[J].江西科学. 1996, 14(4): 223-227.
[23]斯建勇,陈迪华,常琦等.喙果绞股蓝黄酮类化合物的分离及结构测定[J].植物学报. 1994, 36(3): 239-243.
[24]刘鑫燕,魏金美,周蓉.绞股蓝有效成分的提取及抗氧化能力的研究[J].安徽农业科学. 2008, 36 (31) :13670– 13672.
[25]李乐,孙晓东,高小利等.绞股蓝总黄酮对犬急性缺血心肌的保护作用[J].中国病理生理杂志. 2008, 24(2): 388-389.
[26]李乐.绞股蓝总黄酮对离体豚鼠心肌的负性变力作用.上海医科大学学报[J]. 1998, 25(6): 435-437.
[27]邓世林,周晓娟李新凤等.绞股蓝中氨基酸、维生素及多种化学元素的分析[J].湖南医科大学学报, 1994, (6): 487-489.
[28]张袖丽,檀华蓉,胡颖蕙.光叶绞股蓝营养成分的研究[J].安徽师范大学学报(自然科学版).1997, 20(3): 273-276
[29]沈宏伟,肖彦春,车仁国等.绞股蓝化学成分研究的现状[J].时珍国医国药. 2008, 19(7): 1561-1564.
[30]岳琳娜,高学玲,岳鹏翔.绞股蓝有效成分的研究进展[J].综述与述评. 2008, 11(6): 9-11.
[31]刘平贵,王益林.微波消解ICP AES法同时测定绞股蓝中4种微量元素[J].广东微量元素科学. 2008, 15(4): 41-42.
[32] Wang Xiao Wen, Zhang Hua Ping, Chen Feng, et. al. A new lignan from Gynostemma pentaphyllum[J]. Chinese Chemical Letters. 2009, 20: 589–591.
[33]陈业高,魏均娴,左国营.绞股蓝化学成分的研究(II)—脂溶性部分的分离和鉴定[J].昆明医学院学报. 1994, 2(4): 16-19.
[34] Hiroshi Sakamaki, Ken-ichi Itoh, Tetsuyuki Taniai, et. al. Biotransformation of valencene by cultured cells of Gynostemma pentaphyllum[J]. Journal of Molecular Catalysis B: Enzymatic. 2005, 32: 103–106.
[35]覃章铮,赵雷,毕世荣等.绞股蓝的皂甙成分及资源[J].天然产物研究与开发. 1992, 4(1): 83-98.
[36]方乍浦,曾宪仪.绞股蓝酮甙A的化学结构[J].药学学报. 1996, 31(9): 680-683.
[37] Hc LH, Chen ZL, Xie YY. New triterpenoid saponins from Gynostemma pentaphyllum[J]. J. Nat. Prod. 1996, 59(12): 1143–1145.
[38] Hc LH, Chen ZL, Xie YY. DammaRane-type glycosides from Gynostemma pentaphyllum[J]. Phyto chemist Ry.1997, 44(4): 667–670.
[39] Yin F, Hu L, Lou F, Pan R. Dammarane-type glycosides from Gynostemma pentaphyllum[J]. J. Nat. Prod. 2004, 67(6): 942–952.
[40] Yin F, Hu L, Pan R.Novel dammarane-type glycosides from Gynostemma pentaphyllum[J]. Chem. Pharmaceut. Bull. 2004, 52(12): 1440–1444.
[41] Yin F, Zhang Y N, Yang Z Y, et al. Triterpene Saponins from Gynostemma cardiospermum[J]. J. Nat. Prod. 2006, 69: 1394–1398.
[42] Liu-Xin, Ye-Wencai, HsiaoH.W. Wengy, et. Studies on Chemical Constituents of Gynostemma pentaphyllum [J]. Journal of China Pharmaceutical University. 2003, 34(1): 21-23.
[43] Tsunematu Takemoto, Shigenobu Arihara, Kazuko Yoxikawa, et al. Studies on the constituents of cucurbitaceae plants. XIV. On the saponin constituents of Gynostemma Pentophyllum Makino[J]. Yakugaku Zasshi, 1986, 106(8): 664-670.
[44] Kazuko Yoxikawa, Masami Mitake, Tsunematu Takemoto, et al. Studies on the constituents of cucurbitaceae plants. XVIII. On the saponin constituents of Gynostemma Pentophyllum Makino[J]. Yakugaku Zasshi, 1987, 107(5): 361-366.
[45] Tsunematu Takemoto, Shigenobu Arihara, Kazuko Yoxikawa, et al. Studies on the constituents of cucurbitaceae plants. XI. On the saponin constituents of Gynostemma Pentophyllum Makino[J]. Yakugaku Zasshi. 1984, 104(10): 1043-1049.
[46] Tsunematu Takemoto, Shigenobu Arihara, Kazuko Yoxikawa, et al. Studies on the constituents of Gynostemma Pentophyllum Makino. II. Structures of Gypenoside XV-XXI[J]. Yakugaku Zasshi, 1983, 103 (10): 1015-1023.
[47] Hu Lihong, Chen Zhongliang, Xie Yuyuan. Dammarane-type glycosides from Gynostemma pentaphyllum[J]. Phytochemistry. 1997, 44(3): 667-670.
[48] Piacente S, Pizza C. New dammarane-type glycosides from Gynostemma pentaphyllum[J]. J.Nat. Prod. 1995, 58(4): 51.
[49] Yin F, Hu LH. Six new triterpene saponins withα-21, 23-lactone skeleton from Gynostemma pentaphyllum [J]. Helvetica Chimica Acta. 2005, 88(5): 1126.
[50] Yang ZY, Chen QQ, Hu LH. Dammarane-type glycosides from Gynostemma pubescens[J]. Phytochemistry. 2007, 68:1752-1761.
[51] Yin F, Hu LH. Six New Triterpene Saponins with a 21, 23-Lactone Skeleton from Gynostemma pentaphyllum [J]. Helvetica Chimica Acta. 2005, 88(5): 1126.
[52] Yin F, Zhang Y N, Yang Z Y, et al. Nine new dammarane saponins from Gynostemma pentaphyllum[J]. Chemistry& Biodiversity. 2006, 3(7): 771-782.
[53] Norberg A, Khanh H N, Liepinsh E, et al. A novel insulin-releasing substance, phanoside, from the plant Gynostemma pentaphyllum[J]. The Journal of Biological Chemistry. 2004, 1: 31.
[54] Fang Zhapu, Zeng-Xianyi. Structure of Gypentonoside A from Gynostemma Pentaphylum Makino[J]. Acta Pharmaceutica Sinica. 1996, 31(9): 680-683.
[55] Liu X, Yu R M, Hsiao W L, et al. Three New Dammarane Glycosides from Gynostemma pentaphyllum[J]. Chinese Chemical Letters. 2004, 15(1):46-48.
[56] Liu X, Ye W C, Mo Z Y, et al. Five New Ocotillone-Type Saponins from Gynostemma pentaphyllum[J]. J. Nat. Prod. 2004, 67(7): 1147-1151.
[57] Chen Mingho, Chen Shuhsin, Wang Qwafun, et. The molecular mechanism of gypenosides-induced G1 growth arrest of rat hepatic stellate cells[J]. Journal of Ethnopharmacology. 2008,117: 309-317.
[58] W.L.Wendy Hsiao, William Chi Shing Tai, Ziyao Mo, et. al. The anticancer activities and the drug targets of botanical saponins from a medicinal herb Gynostemma pentaphyllum[J]. Journal of Biotechnology. 2008, 136(Supplement 1): S22–S71.
[59] T.H.-W. Huang. M. Bebawy, V.H. Tran, B.D. Roufogalis . Specific reversal of multidrug resistance to colchicine in CEM/VLB100 cells by Gynostemma pentaphyllum extract[J]. Phytomedicine. 2007, 14: 830–839.
[60] Pui KeiWu, Xin Liu, WendyWen-luan Hsiao. The assessment of anti-cancer activities and saponinprofiles of Gynostemma pentaphyllum saponins obtained fromdifferent regions of China[J]. Journal of Biotechnology. 2008, 136(Supplement 1): S85-S86.
[61] William C.S. Tai, W.L.Wendy Hsiao. Chemotherapeutic and potential synergistic effects of Gynostemma pentaphyllum with 5-fluorouracil in Apcmin/+ colorectal cancer mouse model[J]. Journal of Biotechnology. 2008, 136,(Supplement 1): S85-S86.
[62] C. Circosta, R. De Pasquale, F. Occhiuto. Cardiovascular effects of the aqueous extract of Gynostemma pentaphyllum Makino[J]. Phytomedicine 2005,12: 638–643.
[63] Tom Hsun-Wei Huang, Aik Wei Teoha, Bei-Lun Lina, et. al. The Role of Herbal PPAR Modulators in the Treatment of Cardiometabolic Syndrome. Pharmacological Research. Accepted 25 March 2009.
[64] T.H. Huang, Y. Li, V.H. Tran, B.D. Roufogalis. Gypenoside XIX, a natural PPAR-alpha activator, inhibits cytokine-induced vascular cell adhesion molecule-1 (VCAM-1) expression and activity in human endothelial cells[J]. Inflammation and atherosclerosis. European Journal of Pharmacology 2007, 565: 158–165.
[65] Tom Hsun-Wei Huang, Valentina Razmovski-Naumovski, Noeris K. Salam, et. al. A novel LXR-alpha activator identified from the natural product Gynostemma pentaphyllum. Biochem Pharmacol 2005; 70(9): 1298-1308.
[66]刘美玉.绞股蓝皂甙,玉竹水提物对3T3-L1脂肪细胞胰岛素抵抗影响的实验研究[D].北京中医药大学中医学专业硕士学位论文. 2008, 5.
[67] Fugen Aktan, Sheridan Henness, Basil D. Roufogalis, et. al. Gypenosides derived from Gynostemma pentaphyllum suppress NO synthesis in murine macrophages by inhibiting iNOS enzymatic activity and attenuating NF-κB-mediated iNOS protein expression[J]. Nitric Oxide. 2003, 8: 235–242.
[68]许志超,韩凌,赵余庆.绞股蓝总皂苷水解产物中稀有抗肿瘤活性成分的化学研究[J].亚太传统医药. 2008, 11 (4): 41-43.
[69]马建标,赵存祥,范云鸽等.绞股蓝皂苷酸水解次生苷元的分离与鉴定[J].化学学报. 1993, 51: 708-713.
[70]杨崇仁,倪凤仪,周俊,笠井良次.三七中达玛烷型皂甙的热不稳定性及酸水解产物[J].云南植物研究. 1986, 8(1): 87-92.
[71] Teng Rong-Wei, Li Hai-Zhou, Wang De-Zu, et. al Hydrolytic Reaction of Plant Extracts to Generate Molecular Diversity: New Dammarane Glycosides from the Mild Acid Hydrolysate of Root Saponins of Panax notoginseng[J]. 2004, 87: 1270-1278.
[72] Chen Jiang-Tao, Li Hai-Zhou, Wang Dong, et. New Dammarane Monodesmosides from the Acidic Deglycosylation of Notoginseng-Leaf Saponins[J]. Helvetica Chimica Acta. 2006,89: 1442-1448.
[73]赖道万.商陆皂苷及其总苷元的化学成分研究[D].西北大学硕士学位论文. 2008, 6.
[74]刘倩,冯仲杨,郑丽洁等. HPLC检测人参皂苷在温和酸性条件下的降解产物[J].大连医科大学学报. 2000, 22(1): 55-57.
[75]桑原,雅明等.绞股蓝达玛烷皂甙及丙二酸单酰人参皂甙Rb1, Rd和丙二酸单酰绞股蓝皂甙V的分离[J].李春华译自Chem. Pharm. Bull. 1989, 37(1): 135-139.
[76] Wang W, Zhao Y, Rayburn ER, et. In vitro anti-cancer activity and structure–activity relationships of natural products isolated from fruits of Panax ginseng[J]. Cancer Chemother Pharmacol. 2007, 59: 589–601.
[77]宋长春,马兴元,徐景达.用西洋参茎叶总皂甙制取-Rh1和-Rh2[J].中国药学杂志. 1992, 27(1): 6.
[78]刘国臣,李盛钰,何大俊等.甾体皂苷的选择性酸水解研究[J].东北师大学报(自然科学版). 2007, 29(2): 87-91.
[79]张丽萍.苹果多糖的分离纯化及其自由基消除活性于红外光谱分析[D].西北农林科技大学2007届攻读硕士学位研究生学位毕业论文. 2007, 6.
[80]李红,张元湖.应用DPPH法测定苹果提取物的抗氧化能力[J].山东农业大学学报(自然科学版), 2005, 36(1): 35-38
[81]郝晓丽.七种抗氧化剂单一抗氧化活性及其协同作用的研究[D].青岛大学硕士学位论文.2002, 5.
[82]王会,郭立,谢文磊.抗氧化剂抗氧化活性的测定方法[J].食品与发酵工业. 2006, 32(4): 98-102.
[83]郭长江,杨继云,李云峰等. FRAP法测定水果不同部分抗氧化活性[J].中国公共卫生. 2003, 19(7): 841-843.
[84]王会,郭立,谢文磊.抗氧化剂抗氧化活性的测定方法[J].食品与发酵工业. 2006, 32(3): 93-97.
[85]许申鸿.溶剂及pH值对1,1-二苯基-2-苦肼基自由基分析法的影响[J].分析测试学报. 2000, 19(3): 50-52.
[86]于德泉.从天然产物创制新药的发展趋势[J].中国工程科学. 1999, 1(1): 87-90.
[87] Proceeding of 21st IUPAC symposium on the chemistry of nature products[R]. October 11-16th, 1998, Beijing, China.
[88]李旭琴,徐嵩,刘刚.天然产物衍生物化学库的组合合成[J].化学进展, 2006, 09: 95-99.
[89] Alan T., Bull, James E.M. Stach new opportunities for natural product search and discovery. Trends in Microbiology, Volume 2007, 15, (11): 491-499.
[90]贾伊娜.绞股蓝提取物对衰老机体抗氧化能力及DNA损伤影响的实验研究[D].青岛大学硕士学位论文. 2006, 3.
[91] Mackay M.F., Wei J.X., Chen Y.G. Structure of a new dammarane-type triterpene from Gynostemma pentaphyllum (Thurb.) Makino[J].. Crystal Structure Communications.1991, 47(4): 2701.
[92] Ying Wei, Chao-Mei Maa, Masao Hattori. Anti-HIV protease triterpenoids from the acid hydrolysate of Panax ginseng[J]. Phytochemistry Letters. 2009, 2: 63-66.
[2]谭华炳,赵世印,赵斌.绞股蓝的基础研究与组方应用研究概况[J].医学理论与实践, 2005, 18(5): 532-535.
[3]任颖,王秋玉,吴泽民等.绞股蓝皂甙的药理研究进展[J].中国实用中西医杂志,2001,14(1): 988-999.
[4] Wang W, Zhao Y, Rayburn ER, et. al. In vitro anti-cancer activity and structure–activity relationships of natural products isolated from fruits of Panax ginseng[J]. Cancer Chemother Pharmacol. 2007, 59: 589–601.
[5]杨彩霞,王大伟,诸平.竹本常松与绞股蓝[J].宝鸡文理学院学报(自然科学版). 1997, 17(4):53-56.
[6]唐晓玲,蒋桂平,夏培源.绞股蓝粗多糖的提取与初步分析[J].河南医科大学学报. 1996, 31(1): 87-90.
[7] You Lv, Xingbin Yang. Separation and quantification of component monosaccharides of the tea polysaccharides from Gynostemma pentaphyllum by HPLC with indirect UV detection. Food Chemistry. 2009, 112: 742–746.
[8] Chi Ai-Ping, Chen Jin-Ping. Morphological and structural characterization of a polysaccharide from Gynostemma pentaphyllum Makino and its anti-exercise fatigue activity. Carbohydrate Polymers. 2008, 74: 868–874.
[9]王昭晶,罗巅辉.碱提绞股蓝水溶性多糖的研究[J].食品研究与开发. 2006, 27 (5): 92-95.
[10]宋淑亮,吉爱国.绞股蓝多糖的分离纯化及其对神经细胞谷氨酸损伤的保护作用[J].天然产物研究与开发. 2008, 20: 229-232.
[11]罗巅辉,王昭晶.绞股蓝多糖的研究进展[J].生物技术通讯. 2005, 16(6): 703-707.
[12] Zhaojing Wang, Dianhui Luo. Antioxidant activities of di Verent fractions of polysaccharide puri Wed from Gynostemma pentaphyllum Makino. Carbohydrate Polymers. 2007, 68: 54–58.
[13]王海元,池爱平.绞股蓝多糖对运动小鼠组织抗氧化能力的影响.食品科学. 2008, 29(11): 616-619.
[14]沈爱宝,邵健.绞股蓝粗多糖抗癌作用的初步观察[J].南通医学院学报. 1995, 15(1): 148-153.
[15] Rujjanawate C, Kanjanapothi D, Amornlerdpison D. The anti-gastriculcer effect of Gynostemma pentaphyllun Makino[J]. Phytomedicine. 2004, 11:431-435.
[16]娄振岭,陈伟民,马丽萍.绞股蓝多糖对肿瘤细胞的抑制作用.河南医科大学学报[J]. 1996, 31(1): 87-88.
[17]肖增平,吉爱国,宋淑亮等.绞股蓝多糖对小鼠四氯化碳肝损伤的保护作用[J].中国生化药物杂志. 2008, 29(3): 186-188.
[18]宋淑亮,肖增平,吉爱国等.绞股蓝多糖对HepG2细胞酒精性损伤的保护作用[J].生化约物杂志2008, 29(5): 302-306.
[19]陈兢,王喆之.绞股蓝多糖的组成分析及其对质粒DNA的保护作用.中成药. 2009, 31(1): 92-95.
[20]魏守蓉,薛存宽,何学斌.绞股蓝多糖降血糖作用的实验研究.中国老年学杂志. 2005, 25(2):418-420.
[21]王临润,黄明珠.中国东南部4种绞股蓝中黄酮成分的分析[J].中草药. 2007, 38(4): 618-621.
[22]丁建南.疏花绞股蓝黄酮化合物的分离与鉴定[J].江西科学. 1996, 14(4): 223-227.
[23]斯建勇,陈迪华,常琦等.喙果绞股蓝黄酮类化合物的分离及结构测定[J].植物学报. 1994, 36(3): 239-243.
[24]刘鑫燕,魏金美,周蓉.绞股蓝有效成分的提取及抗氧化能力的研究[J].安徽农业科学. 2008, 36 (31) :13670– 13672.
[25]李乐,孙晓东,高小利等.绞股蓝总黄酮对犬急性缺血心肌的保护作用[J].中国病理生理杂志. 2008, 24(2): 388-389.
[26]李乐.绞股蓝总黄酮对离体豚鼠心肌的负性变力作用.上海医科大学学报[J]. 1998, 25(6): 435-437.
[27]邓世林,周晓娟李新凤等.绞股蓝中氨基酸、维生素及多种化学元素的分析[J].湖南医科大学学报, 1994, (6): 487-489.
[28]张袖丽,檀华蓉,胡颖蕙.光叶绞股蓝营养成分的研究[J].安徽师范大学学报(自然科学版).1997, 20(3): 273-276
[29]沈宏伟,肖彦春,车仁国等.绞股蓝化学成分研究的现状[J].时珍国医国药. 2008, 19(7): 1561-1564.
[30]岳琳娜,高学玲,岳鹏翔.绞股蓝有效成分的研究进展[J].综述与述评. 2008, 11(6): 9-11.
[31]刘平贵,王益林.微波消解ICP AES法同时测定绞股蓝中4种微量元素[J].广东微量元素科学. 2008, 15(4): 41-42.
[32] Wang Xiao Wen, Zhang Hua Ping, Chen Feng, et. al. A new lignan from Gynostemma pentaphyllum[J]. Chinese Chemical Letters. 2009, 20: 589–591.
[33]陈业高,魏均娴,左国营.绞股蓝化学成分的研究(II)—脂溶性部分的分离和鉴定[J].昆明医学院学报. 1994, 2(4): 16-19.
[34] Hiroshi Sakamaki, Ken-ichi Itoh, Tetsuyuki Taniai, et. al. Biotransformation of valencene by cultured cells of Gynostemma pentaphyllum[J]. Journal of Molecular Catalysis B: Enzymatic. 2005, 32: 103–106.
[35]覃章铮,赵雷,毕世荣等.绞股蓝的皂甙成分及资源[J].天然产物研究与开发. 1992, 4(1): 83-98.
[36]方乍浦,曾宪仪.绞股蓝酮甙A的化学结构[J].药学学报. 1996, 31(9): 680-683.
[37] Hc LH, Chen ZL, Xie YY. New triterpenoid saponins from Gynostemma pentaphyllum[J]. J. Nat. Prod. 1996, 59(12): 1143–1145.
[38] Hc LH, Chen ZL, Xie YY. DammaRane-type glycosides from Gynostemma pentaphyllum[J]. Phyto chemist Ry.1997, 44(4): 667–670.
[39] Yin F, Hu L, Lou F, Pan R. Dammarane-type glycosides from Gynostemma pentaphyllum[J]. J. Nat. Prod. 2004, 67(6): 942–952.
[40] Yin F, Hu L, Pan R.Novel dammarane-type glycosides from Gynostemma pentaphyllum[J]. Chem. Pharmaceut. Bull. 2004, 52(12): 1440–1444.
[41] Yin F, Zhang Y N, Yang Z Y, et al. Triterpene Saponins from Gynostemma cardiospermum[J]. J. Nat. Prod. 2006, 69: 1394–1398.
[42] Liu-Xin, Ye-Wencai, HsiaoH.W. Wengy, et. Studies on Chemical Constituents of Gynostemma pentaphyllum [J]. Journal of China Pharmaceutical University. 2003, 34(1): 21-23.
[43] Tsunematu Takemoto, Shigenobu Arihara, Kazuko Yoxikawa, et al. Studies on the constituents of cucurbitaceae plants. XIV. On the saponin constituents of Gynostemma Pentophyllum Makino[J]. Yakugaku Zasshi, 1986, 106(8): 664-670.
[44] Kazuko Yoxikawa, Masami Mitake, Tsunematu Takemoto, et al. Studies on the constituents of cucurbitaceae plants. XVIII. On the saponin constituents of Gynostemma Pentophyllum Makino[J]. Yakugaku Zasshi, 1987, 107(5): 361-366.
[45] Tsunematu Takemoto, Shigenobu Arihara, Kazuko Yoxikawa, et al. Studies on the constituents of cucurbitaceae plants. XI. On the saponin constituents of Gynostemma Pentophyllum Makino[J]. Yakugaku Zasshi. 1984, 104(10): 1043-1049.
[46] Tsunematu Takemoto, Shigenobu Arihara, Kazuko Yoxikawa, et al. Studies on the constituents of Gynostemma Pentophyllum Makino. II. Structures of Gypenoside XV-XXI[J]. Yakugaku Zasshi, 1983, 103 (10): 1015-1023.
[47] Hu Lihong, Chen Zhongliang, Xie Yuyuan. Dammarane-type glycosides from Gynostemma pentaphyllum[J]. Phytochemistry. 1997, 44(3): 667-670.
[48] Piacente S, Pizza C. New dammarane-type glycosides from Gynostemma pentaphyllum[J]. J.Nat. Prod. 1995, 58(4): 51.
[49] Yin F, Hu LH. Six new triterpene saponins withα-21, 23-lactone skeleton from Gynostemma pentaphyllum [J]. Helvetica Chimica Acta. 2005, 88(5): 1126.
[50] Yang ZY, Chen QQ, Hu LH. Dammarane-type glycosides from Gynostemma pubescens[J]. Phytochemistry. 2007, 68:1752-1761.
[51] Yin F, Hu LH. Six New Triterpene Saponins with a 21, 23-Lactone Skeleton from Gynostemma pentaphyllum [J]. Helvetica Chimica Acta. 2005, 88(5): 1126.
[52] Yin F, Zhang Y N, Yang Z Y, et al. Nine new dammarane saponins from Gynostemma pentaphyllum[J]. Chemistry& Biodiversity. 2006, 3(7): 771-782.
[53] Norberg A, Khanh H N, Liepinsh E, et al. A novel insulin-releasing substance, phanoside, from the plant Gynostemma pentaphyllum[J]. The Journal of Biological Chemistry. 2004, 1: 31.
[54] Fang Zhapu, Zeng-Xianyi. Structure of Gypentonoside A from Gynostemma Pentaphylum Makino[J]. Acta Pharmaceutica Sinica. 1996, 31(9): 680-683.
[55] Liu X, Yu R M, Hsiao W L, et al. Three New Dammarane Glycosides from Gynostemma pentaphyllum[J]. Chinese Chemical Letters. 2004, 15(1):46-48.
[56] Liu X, Ye W C, Mo Z Y, et al. Five New Ocotillone-Type Saponins from Gynostemma pentaphyllum[J]. J. Nat. Prod. 2004, 67(7): 1147-1151.
[57] Chen Mingho, Chen Shuhsin, Wang Qwafun, et. The molecular mechanism of gypenosides-induced G1 growth arrest of rat hepatic stellate cells[J]. Journal of Ethnopharmacology. 2008,117: 309-317.
[58] W.L.Wendy Hsiao, William Chi Shing Tai, Ziyao Mo, et. al. The anticancer activities and the drug targets of botanical saponins from a medicinal herb Gynostemma pentaphyllum[J]. Journal of Biotechnology. 2008, 136(Supplement 1): S22–S71.
[59] T.H.-W. Huang. M. Bebawy, V.H. Tran, B.D. Roufogalis . Specific reversal of multidrug resistance to colchicine in CEM/VLB100 cells by Gynostemma pentaphyllum extract[J]. Phytomedicine. 2007, 14: 830–839.
[60] Pui KeiWu, Xin Liu, WendyWen-luan Hsiao. The assessment of anti-cancer activities and saponinprofiles of Gynostemma pentaphyllum saponins obtained fromdifferent regions of China[J]. Journal of Biotechnology. 2008, 136(Supplement 1): S85-S86.
[61] William C.S. Tai, W.L.Wendy Hsiao. Chemotherapeutic and potential synergistic effects of Gynostemma pentaphyllum with 5-fluorouracil in Apcmin/+ colorectal cancer mouse model[J]. Journal of Biotechnology. 2008, 136,(Supplement 1): S85-S86.
[62] C. Circosta, R. De Pasquale, F. Occhiuto. Cardiovascular effects of the aqueous extract of Gynostemma pentaphyllum Makino[J]. Phytomedicine 2005,12: 638–643.
[63] Tom Hsun-Wei Huang, Aik Wei Teoha, Bei-Lun Lina, et. al. The Role of Herbal PPAR Modulators in the Treatment of Cardiometabolic Syndrome. Pharmacological Research. Accepted 25 March 2009.
[64] T.H. Huang, Y. Li, V.H. Tran, B.D. Roufogalis. Gypenoside XIX, a natural PPAR-alpha activator, inhibits cytokine-induced vascular cell adhesion molecule-1 (VCAM-1) expression and activity in human endothelial cells[J]. Inflammation and atherosclerosis. European Journal of Pharmacology 2007, 565: 158–165.
[65] Tom Hsun-Wei Huang, Valentina Razmovski-Naumovski, Noeris K. Salam, et. al. A novel LXR-alpha activator identified from the natural product Gynostemma pentaphyllum. Biochem Pharmacol 2005; 70(9): 1298-1308.
[66]刘美玉.绞股蓝皂甙,玉竹水提物对3T3-L1脂肪细胞胰岛素抵抗影响的实验研究[D].北京中医药大学中医学专业硕士学位论文. 2008, 5.
[67] Fugen Aktan, Sheridan Henness, Basil D. Roufogalis, et. al. Gypenosides derived from Gynostemma pentaphyllum suppress NO synthesis in murine macrophages by inhibiting iNOS enzymatic activity and attenuating NF-κB-mediated iNOS protein expression[J]. Nitric Oxide. 2003, 8: 235–242.
[68]许志超,韩凌,赵余庆.绞股蓝总皂苷水解产物中稀有抗肿瘤活性成分的化学研究[J].亚太传统医药. 2008, 11 (4): 41-43.
[69]马建标,赵存祥,范云鸽等.绞股蓝皂苷酸水解次生苷元的分离与鉴定[J].化学学报. 1993, 51: 708-713.
[70]杨崇仁,倪凤仪,周俊,笠井良次.三七中达玛烷型皂甙的热不稳定性及酸水解产物[J].云南植物研究. 1986, 8(1): 87-92.
[71] Teng Rong-Wei, Li Hai-Zhou, Wang De-Zu, et. al Hydrolytic Reaction of Plant Extracts to Generate Molecular Diversity: New Dammarane Glycosides from the Mild Acid Hydrolysate of Root Saponins of Panax notoginseng[J]. 2004, 87: 1270-1278.
[72] Chen Jiang-Tao, Li Hai-Zhou, Wang Dong, et. New Dammarane Monodesmosides from the Acidic Deglycosylation of Notoginseng-Leaf Saponins[J]. Helvetica Chimica Acta. 2006,89: 1442-1448.
[73]赖道万.商陆皂苷及其总苷元的化学成分研究[D].西北大学硕士学位论文. 2008, 6.
[74]刘倩,冯仲杨,郑丽洁等. HPLC检测人参皂苷在温和酸性条件下的降解产物[J].大连医科大学学报. 2000, 22(1): 55-57.
[75]桑原,雅明等.绞股蓝达玛烷皂甙及丙二酸单酰人参皂甙Rb1, Rd和丙二酸单酰绞股蓝皂甙V的分离[J].李春华译自Chem. Pharm. Bull. 1989, 37(1): 135-139.
[76] Wang W, Zhao Y, Rayburn ER, et. In vitro anti-cancer activity and structure–activity relationships of natural products isolated from fruits of Panax ginseng[J]. Cancer Chemother Pharmacol. 2007, 59: 589–601.
[77]宋长春,马兴元,徐景达.用西洋参茎叶总皂甙制取-Rh1和-Rh2[J].中国药学杂志. 1992, 27(1): 6.
[78]刘国臣,李盛钰,何大俊等.甾体皂苷的选择性酸水解研究[J].东北师大学报(自然科学版). 2007, 29(2): 87-91.
[79]张丽萍.苹果多糖的分离纯化及其自由基消除活性于红外光谱分析[D].西北农林科技大学2007届攻读硕士学位研究生学位毕业论文. 2007, 6.
[80]李红,张元湖.应用DPPH法测定苹果提取物的抗氧化能力[J].山东农业大学学报(自然科学版), 2005, 36(1): 35-38
[81]郝晓丽.七种抗氧化剂单一抗氧化活性及其协同作用的研究[D].青岛大学硕士学位论文.2002, 5.
[82]王会,郭立,谢文磊.抗氧化剂抗氧化活性的测定方法[J].食品与发酵工业. 2006, 32(4): 98-102.
[83]郭长江,杨继云,李云峰等. FRAP法测定水果不同部分抗氧化活性[J].中国公共卫生. 2003, 19(7): 841-843.
[84]王会,郭立,谢文磊.抗氧化剂抗氧化活性的测定方法[J].食品与发酵工业. 2006, 32(3): 93-97.
[85]许申鸿.溶剂及pH值对1,1-二苯基-2-苦肼基自由基分析法的影响[J].分析测试学报. 2000, 19(3): 50-52.
[86]于德泉.从天然产物创制新药的发展趋势[J].中国工程科学. 1999, 1(1): 87-90.
[87] Proceeding of 21st IUPAC symposium on the chemistry of nature products[R]. October 11-16th, 1998, Beijing, China.
[88]李旭琴,徐嵩,刘刚.天然产物衍生物化学库的组合合成[J].化学进展, 2006, 09: 95-99.
[89] Alan T., Bull, James E.M. Stach new opportunities for natural product search and discovery. Trends in Microbiology, Volume 2007, 15, (11): 491-499.
[90]贾伊娜.绞股蓝提取物对衰老机体抗氧化能力及DNA损伤影响的实验研究[D].青岛大学硕士学位论文. 2006, 3.
[91] Mackay M.F., Wei J.X., Chen Y.G. Structure of a new dammarane-type triterpene from Gynostemma pentaphyllum (Thurb.) Makino[J].. Crystal Structure Communications.1991, 47(4): 2701.
[92] Ying Wei, Chao-Mei Maa, Masao Hattori. Anti-HIV protease triterpenoids from the acid hydrolysate of Panax ginseng[J]. Phytochemistry Letters. 2009, 2: 63-66.