蒺藜果呋甾皂苷的分离鉴定及含量测定研究
|
摘要
目的:研究蒺藜(Tribulus terrestris L.)果实中呋甾皂苷的分离纯化及结构鉴定,从中选定一种呋甾皂苷作为对照品,并建立该呋甾皂苷含量测定方法,为蒺藜药材的质量提供方法控制。
方法:利用各种现代分离技术,包括大孔树脂、硅胶、ODS、Sephadex LH-20、HPLC等技术,从中药蒺藜果中分离呋甾皂苷类成分,并进一步通过现代波谱技术(1H NMR,13CNMR,ESI-MS,HMBC,HMQC)鉴定呋甾皂苷化合物的结构,并采用反相高效液相色谱法建立蒺藜皂苷K的含量测定方法。
结果:从蒺藜果中分离5个呋甾皂苷化合物,经波谱鉴定了4个呋甾皂苷的结构。4个化合物结构分别为:26-O-β-D-吡喃葡萄糖基-(25R)-5α-呋甾烷-20(22)-烯-12-酮-2α,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅰ);26-O-β-D-吡喃葡萄糖基-(25R)-5α-呋甾烷-20(22)-烯-12-酮-3β,26-二醇-3- O-β-D-吡喃半乳糖糖基(1→2)-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅱ);26-O-β-D-吡喃葡萄糖基-(25S)-5α-呋甾烷-20(22)-烯-12-酮-3β,26-二醇-3 -O-β-D-吡喃半乳糖糖基(1→2)-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅲ);26-O-β-D-吡喃葡萄糖基-(25R)-5α-呋甾烷-20(22)-烯-2α,3β, 26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅳ)。其中选择含量较高纯度在98 %以上的蒺藜皂苷K为对照品,方法学考察证明蒺藜皂苷K在1.1～5.5μg范围内呈良好的线性关系(r = 0.9991),平均回收率为95.76 % (n = 6),RSD = 0.50 %。
结论:化合物Ⅰ为新化合物。5个化合物中,选定化合物Ⅲ(蒺藜皂苷K)作为对照品,建立了蒺藜皂苷K的含量测定方法,结果表明该方法准确、可靠,灵敏度高,重现性好。
Purpose: To study furostanol saponins from the fruits of Tribulus terrestris L. and select terrestrosin K (Ⅲ) as the reference substance to establish the HPLC determination method of its content for the quality control of Tribulus terrestris L..
Method: By the modern chromatography techniques (silica gel, macroporous resin, Sephadex LH-20, ODS and preparative HPLC, etc), furostanol saponins were isolated from the fruits of Tribulus terrestris L.. The structures of these compounds were elucidated by the spectroscopic analysis (1H NMR, 13C NMR, ESIMS, HMQC and HMBC) and chemical methods. High performance liquid chromatography (HPLC) was used to determinate the content of terrestrosin K (Ⅲ).
Result: Five furostanol saponins were isolated from the fruits of Tribulus terrestris L. Four compounds of them were identificated as: 26-O-β-D-glucopyranosyl-(25R)-5α-furostan -20(22)-en-12-one-2α,3β,26-triol-3-O-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside(Ⅰ);26-O-β-D-glucopyranosyl-(25R)-5α-furostan-20(22)–en-12-one-3β,26-diol-3-O-β-D-galacto- pyranosyl-(1→2)-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside(Ⅱ);26-O-β-D-glucopyr-anosyl-(25S)-5α-furostan-20(22)-en-12–one-3β-26-diol-3-O-β-D-galactopyranosyl(1→2)-β- D-glucopyranosyl(1→4)-β-D-galactopyranoside(Ⅲ);26-O-β-D-glucopyranosyl-(25R)-5α-fur- ostan-20(22)-en-2α,3β,26-triol-3-O-β-D-glucopyranosyl(1→2)-β-D-glucopyranosyl(1→4)-β- D-galactopyranoside (Ⅳ). Terrestrosin K (Ⅲ) with high content and purity (﹥98﹪) was selected as the reference substance.The methodology investigation showed that the linearity was obtained over the range of 1.1～5.5μg (r = 0.9991), the average recovery was 95.76 % (n = 6), and RSD = 0.50 %.
Conclusion: CompoundⅠis a new compound. Terrestrosin K (Ⅲ) was selected as the reference substance. The HPLC method of its content determination was established. The method is accurate and reliable, and has a high sensitivity and good reproducibility.
方法:利用各种现代分离技术,包括大孔树脂、硅胶、ODS、Sephadex LH-20、HPLC等技术,从中药蒺藜果中分离呋甾皂苷类成分,并进一步通过现代波谱技术(1H NMR,13CNMR,ESI-MS,HMBC,HMQC)鉴定呋甾皂苷化合物的结构,并采用反相高效液相色谱法建立蒺藜皂苷K的含量测定方法。
结果:从蒺藜果中分离5个呋甾皂苷化合物,经波谱鉴定了4个呋甾皂苷的结构。4个化合物结构分别为:26-O-β-D-吡喃葡萄糖基-(25R)-5α-呋甾烷-20(22)-烯-12-酮-2α,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅰ);26-O-β-D-吡喃葡萄糖基-(25R)-5α-呋甾烷-20(22)-烯-12-酮-3β,26-二醇-3- O-β-D-吡喃半乳糖糖基(1→2)-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅱ);26-O-β-D-吡喃葡萄糖基-(25S)-5α-呋甾烷-20(22)-烯-12-酮-3β,26-二醇-3 -O-β-D-吡喃半乳糖糖基(1→2)-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅲ);26-O-β-D-吡喃葡萄糖基-(25R)-5α-呋甾烷-20(22)-烯-2α,3β, 26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-O-β-D-吡喃葡萄糖基(1→4)-β-D-吡喃半乳糖苷(Ⅳ)。其中选择含量较高纯度在98 %以上的蒺藜皂苷K为对照品,方法学考察证明蒺藜皂苷K在1.1～5.5μg范围内呈良好的线性关系(r = 0.9991),平均回收率为95.76 % (n = 6),RSD = 0.50 %。
结论:化合物Ⅰ为新化合物。5个化合物中,选定化合物Ⅲ(蒺藜皂苷K)作为对照品,建立了蒺藜皂苷K的含量测定方法,结果表明该方法准确、可靠,灵敏度高,重现性好。
Purpose: To study furostanol saponins from the fruits of Tribulus terrestris L. and select terrestrosin K (Ⅲ) as the reference substance to establish the HPLC determination method of its content for the quality control of Tribulus terrestris L..
Method: By the modern chromatography techniques (silica gel, macroporous resin, Sephadex LH-20, ODS and preparative HPLC, etc), furostanol saponins were isolated from the fruits of Tribulus terrestris L.. The structures of these compounds were elucidated by the spectroscopic analysis (1H NMR, 13C NMR, ESIMS, HMQC and HMBC) and chemical methods. High performance liquid chromatography (HPLC) was used to determinate the content of terrestrosin K (Ⅲ).
Result: Five furostanol saponins were isolated from the fruits of Tribulus terrestris L. Four compounds of them were identificated as: 26-O-β-D-glucopyranosyl-(25R)-5α-furostan -20(22)-en-12-one-2α,3β,26-triol-3-O-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside(Ⅰ);26-O-β-D-glucopyranosyl-(25R)-5α-furostan-20(22)–en-12-one-3β,26-diol-3-O-β-D-galacto- pyranosyl-(1→2)-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside(Ⅱ);26-O-β-D-glucopyr-anosyl-(25S)-5α-furostan-20(22)-en-12–one-3β-26-diol-3-O-β-D-galactopyranosyl(1→2)-β- D-glucopyranosyl(1→4)-β-D-galactopyranoside(Ⅲ);26-O-β-D-glucopyranosyl-(25R)-5α-fur- ostan-20(22)-en-2α,3β,26-triol-3-O-β-D-glucopyranosyl(1→2)-β-D-glucopyranosyl(1→4)-β- D-galactopyranoside (Ⅳ). Terrestrosin K (Ⅲ) with high content and purity (﹥98﹪) was selected as the reference substance.The methodology investigation showed that the linearity was obtained over the range of 1.1～5.5μg (r = 0.9991), the average recovery was 95.76 % (n = 6), and RSD = 0.50 %.
Conclusion: CompoundⅠis a new compound. Terrestrosin K (Ⅲ) was selected as the reference substance. The HPLC method of its content determination was established. The method is accurate and reliable, and has a high sensitivity and good reproducibility.
引文
[1]江苏医学院.中药大辞典[M].上海:上海人民出版社, l977, 1274.
[2]中华人民共和国药典(一部)[M].广州:广东科技出版社, 1985, 313.
[3]张健,李俊,莫琪,等.蒺藜提取物的药理研究进展[J].中医药研究, 1998,14(6): 56- 57.
[4] Liu J, Chen H S, Xu Y X, et a1. Studies on chemical Constituents of Tribulus terrestris L.[ J ]. Acad J Second Mil Med Univ(第二军医大学学报), 2003, 24(2): 221-222.
[5] Li J X, Shi Q, Xiong Q B, et a1. Tribulasamides A and B, new hepatoporotective lignan- amides from frutis of Tribulus terrestris: indication of cytoprotectiveactivity inmurine hepatocyte culture [J]. Planta Med, 1998, 64: 628-631.
[6] Wu T S, Shi L S, Kuo S C. Alkaloids and other constituents from Tribulus terrestris [J]. Phytochemistry, 1999, 50: 1411-1415.
[7] Chen H S, Chen Q J, Xuan W D. A new organic acid from Tribulus terrestris [J]. Acad J Second Mil Med Univ(第二军医大学学报), 2004, 25(11): 1241-1242.
[8] Huang X L, Zhang Y S, Liang Z Y. Studies on water soluble polysaccharides isolated from Tribulus terrestris-purification and preliminary structural determination of heter- opoly saccaride H [J]. Acta Pharm Sin(药学学报), 1991, 26(8): 578-583.
[9]钱本余.蒺藜研究概述[J].中成药, 1990, 12(1): 34.
[10] Gheorghiu A, Ionescu-Matiu E. Presence of chlorogenin next to diosgenin and gitogenin in Tribulus terrestris. Ann Pharm, 1968; 26: 745-798.
[11] De Kock W T, Enslin P R. Chemical investigation of photosensitization diseases of domestric animals I. Isolation and characterization of steroidal sapogenins from Tribulus terrestris. Aft Chem Inst, 1958; 11(2): 33-36.
[12]徐一新,陈海生,梁华清,等.蒺藜的心血管活性成分的研究.第二军医大学学报, 1998; 19(4): 380.
[13] Xu Yi-Xin, Chen Hai-Sheng, Liu Wen-Yong, et al. Tow Sapogenins from Tribulus Terrestris. Phytochemisty, 1998; 49(1): 199-201.
[14]黄金文,蒋山好,谭昌恒,等.蒺藜甾体皂甙元化学成分研究.天然产物研究与开发, 2003; 15(2): 101.
[15] Huang H W, Jiang S H, Tan CH, et al. Structural elucidation of three new steroid sapogenins. Chin J Org Chem, 2002; 22, 917-921.
[16] Huang J W, Tan C H, Jiang S H, et a1. Terrestrinins A and B, two new steroid saponins from Tribulus terrestris. Assian Nat Prod Res, 2003; 5: 285-290.
[17] WuGong, J Shanhao, J Fuxiang, et a1.Steroid Glycosides from tribulus terrestris. Phyto- chemistry, 1996; 42(6): 1677-1681.
[18] Xu Yi-Xin, Chen Hai-Sheng, Liang Hua-Qing, et al. Three new Saponins from Tribulus terrestris. Planta Med. 2000; 66: 545-550.
[19]金京玲,金永日,徐雅娟,等.刺蒺藜果实中两种甾体皂甙的分离与鉴定.中草药, 2000; 31(2): 90.
[20] Wangyan, Kazuhiro chtani, Ryoji Kasal, et al.Steroida sapoinins from fruits of T.te rrstris. Phytochemistry, 1996; 42(5): 1417-1422.
[21] Deepak M, Dipankar G, Prashanth D, et a1. Tribulosin and bsitosterol dglucoside the anthelmintic principles of Tribulus terrestris. Phytomedicine, 2002; 9: 753-756.
[22] Cai L, Wu Y, Zhang J, Steroidal saponins from Ttibulus terrestris. Planta Med, 2001; 67: 196-198.
[23]徐雅娟,谢生旭,赵洪峰,等.蒺藜果中两种新甾体皂甙的分离和鉴定.药学学报, 2001; 36(10): 750-753.
[24] Mahato S B, Sahu N P, Ganguiy A N, et al. Steroidal glycosides of Ttibulus terrestris Linn.. Chem Soc Perkin I, 1981; 9: 2405-2410.
[25] Emal Bedlr, Ikhlas A.Khan. New steroidal glycosides from the fruits of T.terrestris. Joumal of natural Products, 2000; 63(12): 1699-1701.
[26] Sharma H C, Narula J L. Chemical investigation of flowers of Tribulus terrestris. Chem Era, 1977; 13: 15-17.
[27] Wang Y, Othtani K, Kasai R, et a1. Steroida1 saponins fromfruits of Tribulus terrestris. Phytochemistry, 1997, 45: 811-881.
[28] PerepelktsaE.D.:Kintya, P.K.Khin. Prir.Soedin, 1975; 11(2): 260.
[29] Mahato, Shashi, B.:Sahu, et al. J.Chem.Soc. Perkin.Tran, 1981; 11(9): 2405-2410.
[30] Tomova M, Panova D, Wulfson N S. Steroid saponins andsapogeninsⅣ.Saponins fromTribulus terrestris. Planta Med, 1974; 25: 231-237.
[31] Conrad J, Dinchev D, Klaiber I, et al. A novel furostanol saponin from Tribulus terrestris of Bulgarian origin. Fitoterapia, 2004; 75: 117-122.
[32] Matschenko H E, Gulemetova R, Kintya P K, et a1. A sulfated glycoside from the preparation“Tribestan”. Khim Prir Soedin, 1990; 5: 649-652.
[33] Wangyan, Kazuhiro chtani, Ryoji Kasal, et a1. Steroida sapoinins from fruits of T.terrstris. Phytochemistry, 1997; 45(4): 811-817.
[34] Cai Li-Feng, Zhang Jian-Guo, Xu Ya-Juan, et al. Acta Pharmaceutica Sinica . 1999; 34 (10): 759-761.
[35] Huang JW, Tan CH, Jiang SH. Terrestrinins A and B, two new steroid saponins from Tribulus terrestris. Jaisan Nat Prod Res, 2003; 5(4): 285-290.
[36] Wilkins A L,Miles C O,De Kock W T,et a1,Photosensitivity in South Agrica. IX. Structure elucidation of a beta-glucosidease-treated saponin from Tribulus terrestris and the identification of saponin chemotypes of South AgricanT.terrestris. 0nderstepoort J Vet Res, l996; 63: 327-334.
[37] Bedir E, Khan I A, Walker L A. Biologically active steroidal glycosides from Tribulus terrestris. Pharmazie, 2002; 57: 491-493.
[38] Kostova I, Dinchev D, Rentsch GH, et al. Two new sulfated furostanol saponins from Tribulus terrestris. Z Naturforsch[C], 2002; 57(1-2):33-38.
[39] Conrad j, Dinchev D, Klaiberl, et al. A novel furostanol saponin from Tribulus terrestris of bulgarian origin. Fitoterapoa, 2004; 75(2): 117-122.
[40]王艳.刺蒺藜药理作用及化学成分的研究概况.北京中医学院学报, 1989; 12(6): 30-33.
[41] Li Jiao-xin, QiSh, Xiong Quan-Bo, et a1. Tribulusamide A and B, new Hepatoprotec five Lignanamides from the Fruits of Tribulus terrestris Indication of Cytoprotecfive Activity in Murine tlepatoeyte Culture. Planta Mdica, 1988; 64(7): 628-631.
[42]师勤,马果玉,徐珞珊,等.比色法测定蒺藜中多糖的含量[J].中国药科大学学报, 1997, 28(5): 291-293.
[43]师勤,余伯阳,徐珞珊,等.反高效液相色谱法测定蒺藜类3种水解黄酮甙元的含量.药物分析杂志, 1999; 19(2): 75-78.
[44]王学东,邵健新,翟筱,等.蒺藜中氨基酸含量的测定.氨基酸杂志, 1994; (2): 29-30.
[45]陈海生,陈前进,宣伟东.蒺藜中一个新的有机酸成分的分离与鉴定.第二军医大学学报, 2004; 25(11): 1241.
[46]苏卫东,徐雅娟.蒺藜的研究进展.长春中医药大学学报, 2006; 22(3): 72-74.
[47]程纯,徐济民.蒺藜抗心肌缺氧再给氧损伤的实验研究[J].上海第二医科大学学报, 1993, 13(2): l74-176.
[48]曲娴,刘建平,赵素文,等.蒺藜总皂甙对AMI家兔血清SOD和MDA变化的影响[J].中国病理生理杂志, 2001, l7(11): 1055.
[49]陈慧敏.心脑舒通抗衰老29例临床观察[J].实用老年医学, 1993, 7(3): 140.
[50]杨学义,韩宝福,崔世贞,等.心脑舒通的药理和临床应用[J].新药与临床, 1992, l1(6): 342-345.
[51]李明娟,瞿伟菁,褚书地,等.蒺藜水煎剂对小鼠糖代谢中糖异生的作用[J].中药材, 2001, 24(8): 586-588.
[52]冯玛莉,李宝平,武玉鹏,等.蒺藜的降血糖作用[J].中草药, 1998, 29(2): 107.
[53] Zhang J D, Xu Z, Cao Y B. Antifungal activities and action mechanisms of compounds from Tribulus terrestris. Ethnopharmacol, 2006; 10: 76-84.
[54]孙斌,瞿伟菁,柏忠江.蒺藜皂苷对乳腺癌细胞Bcap-37的体外抑制作用[J].中药材, 2003, 26(2): 104-106.
[55] Adimoelja A. Phytochemicals and the breckthrough of traditional herbs in the managem- ent of sexual dysfunctions. Int Jandrol, 2002; 23(2): 82-84.
[56] Gauthaman K, Adaikan P G, Prasad N V. Aphrodisiacproperties of Tribulus terrestris extract (protodioscin) in normal and castrated rats. Life Sci, 2002; 71: 1385-1396.
[57]叶长华,蒋幼芹,江冰.白蒺藜醇甙对混合培养鼠视网膜神经细胞的作用[J].眼视光学研究, 2001, 3(3): 148-151.
[58]李艳莉,钟理,梁丽红. 6种中药抑制酪氨酸酶活性的研究.时珍国医国药, 2002; 13 (3):129-131.
[59] Bourke CA, Sterens GR, Carrigan MT. Locmotor effects in sheep of Alkaloids identified in Austrfian T.terrestris. Australian Veterinary Joumal, 1992; 69(7): 163-165.
[60]师勤,汤依群,徐路珊,等.硬软蒺藜药效学比较.上海第二医科大学学报, 2000;20(10): 44-45.
[61]王博文.蒺藜皂苷治疗冠心病心绞痛406例临床观察[J].中西医结合杂志, 1990, 10(2): 85.
[62]杨仓良.毒药本草[M].北京:中国中医药出版社, 1993, 736.
[63]王发渭.高辉运变通古方创新拾贝[J].新中医, 1994, 26(1): 4.
[64]张秀琴.蒺藜总皂苷抗衰老作用研究[J].中药材, 1990, 13(2): 34.
[65]舒国伟,吕嘉枥,陈合.比色法测定蒺藜甾体皂苷的研究.食品工业科技, 2006; 8: 182.
[66]张菊红,王志伟,金吉琴,等.蒺藜全草中总皂苷总含量的测定.中国临床药学杂志, 2001; 10(4):244.
[67]李瑞海,杨松松.蒺藜总皂苷含量测定方法研究.实用药物与临床, 2006;9(2):77.
[68]王桂玲,解生旭,赵宏峰,等. HPLC-蒸发光散射检测法测定蒺藜中蒺藜皂苷A.中草药, 2005; 36(9): 1406-1407.
[69]祁海宏,王春,严伟民.高效液相色谱法-蒸发光散射检测测定蒺藜皂苷1的含量.中国药事, 2006; 20(3): 158.
[70]余晓红. HPLC测定刺蒺藜总皂苷中的薯蓣皂苷元.华西药学杂志, 2008; 23(4): 474-475
[71] Agerawal. Pawan K. Phytochemistry, 1992; 31(10): 3307-3330.
[72] Chiristian W., Matthias H., Olaf K., et al. Helvetica Chimica Acta, 2000; 83: 1454-1465.
[73] Angarawa P.K., Jian D.C., Gupta R.K. et.al. Phytochemistry, 1985; 24(11): 2497-2520.
[74] Agrarl PK, et al. Magnetic Resonance in Chemistry, 1995; 33: 923-953.
[75] Wang Yan, Ohtani K., Kasai R, et. al. Phytochemistry, 1997; 45(4): 811-817.
[76] Yoshikawa M., Murakami T., Komatsu H, et al. Chem.Pharm.Bull, 1997; 45(1): 81-87.
[77] Lan Su, Gang Chen, Sheng Guang Feng, et al. Steroids, 2008;待发.
[2]中华人民共和国药典(一部)[M].广州:广东科技出版社, 1985, 313.
[3]张健,李俊,莫琪,等.蒺藜提取物的药理研究进展[J].中医药研究, 1998,14(6): 56- 57.
[4] Liu J, Chen H S, Xu Y X, et a1. Studies on chemical Constituents of Tribulus terrestris L.[ J ]. Acad J Second Mil Med Univ(第二军医大学学报), 2003, 24(2): 221-222.
[5] Li J X, Shi Q, Xiong Q B, et a1. Tribulasamides A and B, new hepatoporotective lignan- amides from frutis of Tribulus terrestris: indication of cytoprotectiveactivity inmurine hepatocyte culture [J]. Planta Med, 1998, 64: 628-631.
[6] Wu T S, Shi L S, Kuo S C. Alkaloids and other constituents from Tribulus terrestris [J]. Phytochemistry, 1999, 50: 1411-1415.
[7] Chen H S, Chen Q J, Xuan W D. A new organic acid from Tribulus terrestris [J]. Acad J Second Mil Med Univ(第二军医大学学报), 2004, 25(11): 1241-1242.
[8] Huang X L, Zhang Y S, Liang Z Y. Studies on water soluble polysaccharides isolated from Tribulus terrestris-purification and preliminary structural determination of heter- opoly saccaride H [J]. Acta Pharm Sin(药学学报), 1991, 26(8): 578-583.
[9]钱本余.蒺藜研究概述[J].中成药, 1990, 12(1): 34.
[10] Gheorghiu A, Ionescu-Matiu E. Presence of chlorogenin next to diosgenin and gitogenin in Tribulus terrestris. Ann Pharm, 1968; 26: 745-798.
[11] De Kock W T, Enslin P R. Chemical investigation of photosensitization diseases of domestric animals I. Isolation and characterization of steroidal sapogenins from Tribulus terrestris. Aft Chem Inst, 1958; 11(2): 33-36.
[12]徐一新,陈海生,梁华清,等.蒺藜的心血管活性成分的研究.第二军医大学学报, 1998; 19(4): 380.
[13] Xu Yi-Xin, Chen Hai-Sheng, Liu Wen-Yong, et al. Tow Sapogenins from Tribulus Terrestris. Phytochemisty, 1998; 49(1): 199-201.
[14]黄金文,蒋山好,谭昌恒,等.蒺藜甾体皂甙元化学成分研究.天然产物研究与开发, 2003; 15(2): 101.
[15] Huang H W, Jiang S H, Tan CH, et al. Structural elucidation of three new steroid sapogenins. Chin J Org Chem, 2002; 22, 917-921.
[16] Huang J W, Tan C H, Jiang S H, et a1. Terrestrinins A and B, two new steroid saponins from Tribulus terrestris. Assian Nat Prod Res, 2003; 5: 285-290.
[17] WuGong, J Shanhao, J Fuxiang, et a1.Steroid Glycosides from tribulus terrestris. Phyto- chemistry, 1996; 42(6): 1677-1681.
[18] Xu Yi-Xin, Chen Hai-Sheng, Liang Hua-Qing, et al. Three new Saponins from Tribulus terrestris. Planta Med. 2000; 66: 545-550.
[19]金京玲,金永日,徐雅娟,等.刺蒺藜果实中两种甾体皂甙的分离与鉴定.中草药, 2000; 31(2): 90.
[20] Wangyan, Kazuhiro chtani, Ryoji Kasal, et al.Steroida sapoinins from fruits of T.te rrstris. Phytochemistry, 1996; 42(5): 1417-1422.
[21] Deepak M, Dipankar G, Prashanth D, et a1. Tribulosin and bsitosterol dglucoside the anthelmintic principles of Tribulus terrestris. Phytomedicine, 2002; 9: 753-756.
[22] Cai L, Wu Y, Zhang J, Steroidal saponins from Ttibulus terrestris. Planta Med, 2001; 67: 196-198.
[23]徐雅娟,谢生旭,赵洪峰,等.蒺藜果中两种新甾体皂甙的分离和鉴定.药学学报, 2001; 36(10): 750-753.
[24] Mahato S B, Sahu N P, Ganguiy A N, et al. Steroidal glycosides of Ttibulus terrestris Linn.. Chem Soc Perkin I, 1981; 9: 2405-2410.
[25] Emal Bedlr, Ikhlas A.Khan. New steroidal glycosides from the fruits of T.terrestris. Joumal of natural Products, 2000; 63(12): 1699-1701.
[26] Sharma H C, Narula J L. Chemical investigation of flowers of Tribulus terrestris. Chem Era, 1977; 13: 15-17.
[27] Wang Y, Othtani K, Kasai R, et a1. Steroida1 saponins fromfruits of Tribulus terrestris. Phytochemistry, 1997, 45: 811-881.
[28] PerepelktsaE.D.:Kintya, P.K.Khin. Prir.Soedin, 1975; 11(2): 260.
[29] Mahato, Shashi, B.:Sahu, et al. J.Chem.Soc. Perkin.Tran, 1981; 11(9): 2405-2410.
[30] Tomova M, Panova D, Wulfson N S. Steroid saponins andsapogeninsⅣ.Saponins fromTribulus terrestris. Planta Med, 1974; 25: 231-237.
[31] Conrad J, Dinchev D, Klaiber I, et al. A novel furostanol saponin from Tribulus terrestris of Bulgarian origin. Fitoterapia, 2004; 75: 117-122.
[32] Matschenko H E, Gulemetova R, Kintya P K, et a1. A sulfated glycoside from the preparation“Tribestan”. Khim Prir Soedin, 1990; 5: 649-652.
[33] Wangyan, Kazuhiro chtani, Ryoji Kasal, et a1. Steroida sapoinins from fruits of T.terrstris. Phytochemistry, 1997; 45(4): 811-817.
[34] Cai Li-Feng, Zhang Jian-Guo, Xu Ya-Juan, et al. Acta Pharmaceutica Sinica . 1999; 34 (10): 759-761.
[35] Huang JW, Tan CH, Jiang SH. Terrestrinins A and B, two new steroid saponins from Tribulus terrestris. Jaisan Nat Prod Res, 2003; 5(4): 285-290.
[36] Wilkins A L,Miles C O,De Kock W T,et a1,Photosensitivity in South Agrica. IX. Structure elucidation of a beta-glucosidease-treated saponin from Tribulus terrestris and the identification of saponin chemotypes of South AgricanT.terrestris. 0nderstepoort J Vet Res, l996; 63: 327-334.
[37] Bedir E, Khan I A, Walker L A. Biologically active steroidal glycosides from Tribulus terrestris. Pharmazie, 2002; 57: 491-493.
[38] Kostova I, Dinchev D, Rentsch GH, et al. Two new sulfated furostanol saponins from Tribulus terrestris. Z Naturforsch[C], 2002; 57(1-2):33-38.
[39] Conrad j, Dinchev D, Klaiberl, et al. A novel furostanol saponin from Tribulus terrestris of bulgarian origin. Fitoterapoa, 2004; 75(2): 117-122.
[40]王艳.刺蒺藜药理作用及化学成分的研究概况.北京中医学院学报, 1989; 12(6): 30-33.
[41] Li Jiao-xin, QiSh, Xiong Quan-Bo, et a1. Tribulusamide A and B, new Hepatoprotec five Lignanamides from the Fruits of Tribulus terrestris Indication of Cytoprotecfive Activity in Murine tlepatoeyte Culture. Planta Mdica, 1988; 64(7): 628-631.
[42]师勤,马果玉,徐珞珊,等.比色法测定蒺藜中多糖的含量[J].中国药科大学学报, 1997, 28(5): 291-293.
[43]师勤,余伯阳,徐珞珊,等.反高效液相色谱法测定蒺藜类3种水解黄酮甙元的含量.药物分析杂志, 1999; 19(2): 75-78.
[44]王学东,邵健新,翟筱,等.蒺藜中氨基酸含量的测定.氨基酸杂志, 1994; (2): 29-30.
[45]陈海生,陈前进,宣伟东.蒺藜中一个新的有机酸成分的分离与鉴定.第二军医大学学报, 2004; 25(11): 1241.
[46]苏卫东,徐雅娟.蒺藜的研究进展.长春中医药大学学报, 2006; 22(3): 72-74.
[47]程纯,徐济民.蒺藜抗心肌缺氧再给氧损伤的实验研究[J].上海第二医科大学学报, 1993, 13(2): l74-176.
[48]曲娴,刘建平,赵素文,等.蒺藜总皂甙对AMI家兔血清SOD和MDA变化的影响[J].中国病理生理杂志, 2001, l7(11): 1055.
[49]陈慧敏.心脑舒通抗衰老29例临床观察[J].实用老年医学, 1993, 7(3): 140.
[50]杨学义,韩宝福,崔世贞,等.心脑舒通的药理和临床应用[J].新药与临床, 1992, l1(6): 342-345.
[51]李明娟,瞿伟菁,褚书地,等.蒺藜水煎剂对小鼠糖代谢中糖异生的作用[J].中药材, 2001, 24(8): 586-588.
[52]冯玛莉,李宝平,武玉鹏,等.蒺藜的降血糖作用[J].中草药, 1998, 29(2): 107.
[53] Zhang J D, Xu Z, Cao Y B. Antifungal activities and action mechanisms of compounds from Tribulus terrestris. Ethnopharmacol, 2006; 10: 76-84.
[54]孙斌,瞿伟菁,柏忠江.蒺藜皂苷对乳腺癌细胞Bcap-37的体外抑制作用[J].中药材, 2003, 26(2): 104-106.
[55] Adimoelja A. Phytochemicals and the breckthrough of traditional herbs in the managem- ent of sexual dysfunctions. Int Jandrol, 2002; 23(2): 82-84.
[56] Gauthaman K, Adaikan P G, Prasad N V. Aphrodisiacproperties of Tribulus terrestris extract (protodioscin) in normal and castrated rats. Life Sci, 2002; 71: 1385-1396.
[57]叶长华,蒋幼芹,江冰.白蒺藜醇甙对混合培养鼠视网膜神经细胞的作用[J].眼视光学研究, 2001, 3(3): 148-151.
[58]李艳莉,钟理,梁丽红. 6种中药抑制酪氨酸酶活性的研究.时珍国医国药, 2002; 13 (3):129-131.
[59] Bourke CA, Sterens GR, Carrigan MT. Locmotor effects in sheep of Alkaloids identified in Austrfian T.terrestris. Australian Veterinary Joumal, 1992; 69(7): 163-165.
[60]师勤,汤依群,徐路珊,等.硬软蒺藜药效学比较.上海第二医科大学学报, 2000;20(10): 44-45.
[61]王博文.蒺藜皂苷治疗冠心病心绞痛406例临床观察[J].中西医结合杂志, 1990, 10(2): 85.
[62]杨仓良.毒药本草[M].北京:中国中医药出版社, 1993, 736.
[63]王发渭.高辉运变通古方创新拾贝[J].新中医, 1994, 26(1): 4.
[64]张秀琴.蒺藜总皂苷抗衰老作用研究[J].中药材, 1990, 13(2): 34.
[65]舒国伟,吕嘉枥,陈合.比色法测定蒺藜甾体皂苷的研究.食品工业科技, 2006; 8: 182.
[66]张菊红,王志伟,金吉琴,等.蒺藜全草中总皂苷总含量的测定.中国临床药学杂志, 2001; 10(4):244.
[67]李瑞海,杨松松.蒺藜总皂苷含量测定方法研究.实用药物与临床, 2006;9(2):77.
[68]王桂玲,解生旭,赵宏峰,等. HPLC-蒸发光散射检测法测定蒺藜中蒺藜皂苷A.中草药, 2005; 36(9): 1406-1407.
[69]祁海宏,王春,严伟民.高效液相色谱法-蒸发光散射检测测定蒺藜皂苷1的含量.中国药事, 2006; 20(3): 158.
[70]余晓红. HPLC测定刺蒺藜总皂苷中的薯蓣皂苷元.华西药学杂志, 2008; 23(4): 474-475
[71] Agerawal. Pawan K. Phytochemistry, 1992; 31(10): 3307-3330.
[72] Chiristian W., Matthias H., Olaf K., et al. Helvetica Chimica Acta, 2000; 83: 1454-1465.
[73] Angarawa P.K., Jian D.C., Gupta R.K. et.al. Phytochemistry, 1985; 24(11): 2497-2520.
[74] Agrarl PK, et al. Magnetic Resonance in Chemistry, 1995; 33: 923-953.
[75] Wang Yan, Ohtani K., Kasai R, et. al. Phytochemistry, 1997; 45(4): 811-817.
[76] Yoshikawa M., Murakami T., Komatsu H, et al. Chem.Pharm.Bull, 1997; 45(1): 81-87.
[77] Lan Su, Gang Chen, Sheng Guang Feng, et al. Steroids, 2008;待发.