粗茎秦艽Gentiana crassicaulis Duthie ex Bruk.及其生物碱类成分研究
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摘要
秦艽Radix Gentianae Macrophyllae来源于龙胆科植物秦艽Gentiana macrophylla Pall.、粗茎秦艽G. crassicaulis Duthie ex Burk.、麻花秦艽G. straminea Maxim.、或小秦艽G. dahurica Fisch.。生药秦艽具有祛风湿、清湿热、止痹痛的功能。临床上用于风湿痹痛、筋脉拘挛、骨节烦痛、日曝潮热和小儿疳积发热等症。秦艽主产于甘肃、青海、四川、陕西等省。四川中药志记载的秦艽主要原植物之一是粗茎秦艽,四川市场上流通的“萝卜艽”也主要来源于粗茎秦艽。
秦艽主要含裂环烯醚萜苷、甾醇苷、挥发油和糖类等成分。如在提取过程中加入氨,裂环烯醚萜苷类成分即转化成生物碱类成分。该类生物碱具有抗风湿、止痛等药理作用,与中药秦艽的效用基本一致;并且秦艽总碱提取物的抗炎镇痛作用强于秦艽总苷提取物。目前对秦艽的研究工作主要集中在秦艽Gentiana macrophylly Pall.上,在化学成分方面侧重于对裂环烯醚萜苷和甾醇苷等成分的研究;而对粗茎秦艽G. crassicaulis Duthie ex Burk.的研究较少。据此,本课题进行了
Radix Gentianae Macrophyllae is derived from the Gentiana species such as Gentiana macrophylla Pall., G. crassicaulis Duthie ex Burk., G. straminea Maxim., or G. dahurica Fisch.. Radix Gentianae Macrophyllae is quite frequently used for the treatment of rheumatism, pain, fungal and bacterial infections, hepatitis and hypertension. It is distributed over Gansu, Qinghai, Sichuan, and Shanxi. The Chinese crude drug "Qinjiao" which was reported in "Sichuan Zhong Yao Zhi" and the commodity "Luobojiqo" in Sichuan market both come from the roots of G. crassicaulis Duthie ex Burk.,Radix Gentianae Macrophyllae mainly contains secoiridoide glycoside, sterol glycoside, Volatile oil and carbohydrate. Previous research revealed that secoiridoide glycosides were transformed to alkaloids due to the presence of amine in the isolation process. The alkaloids have depressive effects on rheumatism, pain, fungal and bacterial infections as same as Radix Gentianae Macrophyllae. Previous researchs on G. macrophylla Pall, are far more than G.
crassicaulis Duthie ex Burk..In this paper, the pharmacognostical studies on G. crassicaulis Duthie ex Burk. are reported, including external structures and morphological characters .10 components first time were extracted with amine and isolated from roots of G. crassicaulis Duthie ex Burk.. The structures of 8 alkaloids have been established to be gentianine, gentianal, gentiatibetine, gentiocrasine, gentiocrasidine, daucosterol, p-sitosterol and plamitic acid by spectroscopic analysis('H-NMR, I3C-NMR, DEPT, ESIMS, IR, UV)and chemical evidence respectively, gentiocrasine and gentiocrasidine was isolated for the first time.Gentianine and gentianal are the major biologically active alkaloids in Radix Gentianae Macrophyllae, and gentiopicroside is the major biologically active component in it. The content of total alkaloids was determined by silicoduo-decitungstic acid titration. The result is G. macrophylla Pall>G. crassicaulis Duthie ex Burk. >G. straminea Maxim. .An RP-HPLC assay was developed for determining gentianine, gentianal and gentiopicroside. The sensitive and specific assay was successfully utilized to quantify the 3 biologically active components. The result is gentiopicroside >gentianine>gentianal. in several Gentiana species.
秦艽主要含裂环烯醚萜苷、甾醇苷、挥发油和糖类等成分。如在提取过程中加入氨,裂环烯醚萜苷类成分即转化成生物碱类成分。该类生物碱具有抗风湿、止痛等药理作用,与中药秦艽的效用基本一致;并且秦艽总碱提取物的抗炎镇痛作用强于秦艽总苷提取物。目前对秦艽的研究工作主要集中在秦艽Gentiana macrophylly Pall.上,在化学成分方面侧重于对裂环烯醚萜苷和甾醇苷等成分的研究;而对粗茎秦艽G. crassicaulis Duthie ex Burk.的研究较少。据此,本课题进行了
Radix Gentianae Macrophyllae is derived from the Gentiana species such as Gentiana macrophylla Pall., G. crassicaulis Duthie ex Burk., G. straminea Maxim., or G. dahurica Fisch.. Radix Gentianae Macrophyllae is quite frequently used for the treatment of rheumatism, pain, fungal and bacterial infections, hepatitis and hypertension. It is distributed over Gansu, Qinghai, Sichuan, and Shanxi. The Chinese crude drug "Qinjiao" which was reported in "Sichuan Zhong Yao Zhi" and the commodity "Luobojiqo" in Sichuan market both come from the roots of G. crassicaulis Duthie ex Burk.,Radix Gentianae Macrophyllae mainly contains secoiridoide glycoside, sterol glycoside, Volatile oil and carbohydrate. Previous research revealed that secoiridoide glycosides were transformed to alkaloids due to the presence of amine in the isolation process. The alkaloids have depressive effects on rheumatism, pain, fungal and bacterial infections as same as Radix Gentianae Macrophyllae. Previous researchs on G. macrophylla Pall, are far more than G.
crassicaulis Duthie ex Burk..In this paper, the pharmacognostical studies on G. crassicaulis Duthie ex Burk. are reported, including external structures and morphological characters .10 components first time were extracted with amine and isolated from roots of G. crassicaulis Duthie ex Burk.. The structures of 8 alkaloids have been established to be gentianine, gentianal, gentiatibetine, gentiocrasine, gentiocrasidine, daucosterol, p-sitosterol and plamitic acid by spectroscopic analysis('H-NMR, I3C-NMR, DEPT, ESIMS, IR, UV)and chemical evidence respectively, gentiocrasine and gentiocrasidine was isolated for the first time.Gentianine and gentianal are the major biologically active alkaloids in Radix Gentianae Macrophyllae, and gentiopicroside is the major biologically active component in it. The content of total alkaloids was determined by silicoduo-decitungstic acid titration. The result is G. macrophylla Pall>G. crassicaulis Duthie ex Burk. >G. straminea Maxim. .An RP-HPLC assay was developed for determining gentianine, gentianal and gentiopicroside. The sensitive and specific assay was successfully utilized to quantify the 3 biologically active components. The result is gentiopicroside >gentianine>gentianal. in several Gentiana species.
引文
[1] 中华人民共和国国家药典委员会.中国药典(一部)[M].北京:化学工业出版社,2000.222
[2] 魏·吴晋等.神农本草经(重排本)[M].北京:人民卫生出版社,1982.67
[3] 粱·陶弘景.名医别录(辑校本)[M].北京:人民卫生出版社,1986.113
[4] 夏光成,萧培根,马毓泉.中药秦艽原植物的研究.药学学报,1965,12(6):399～411
[5] 刘艳红,李兴从,刘玉清,等.秦艽中的环烯醚萜甙成分[J].云南植物研究,1994,16(1):85～89
[6] 中国医科学院药物研究所.中草药有效成分研究(第一版),第一分册[M].北京:人民卫生出版社,1972.390
[7] Kubota T, Tomita Y. Derivation of gentianin from swertiamarin [J]. Tetrahedron Letters, 1961, 14: 453～454
[8] 林辉明.科植物基源生藥研究(第1報)中味成分Gentiopicroside定量[J].药学杂志(日),1976,96(3):356～361
[9] 郭亚健,陆蕴如.龙胆苦甙转化为秦艽丙素等生物碱的研究[J].药物分析杂志,1983,3(5):268～271
[10] 蔡宝蕴,穆芾芳,李文兰,等.秦艽生物碱提取新工艺[J].中草药,1986,17(3):15～16
[11] 王英,楼之岑.中药秦艽的研究概况[J].药学通报,1987,22(3):153～156
[12] 籍秀娟,刘耕陶,宋振玉.秦艽生物碱甲的药理作用Ⅱ.秦艽生物碱甲的抗炎作用及与一些临床有效药物的比较[J].生理学报,1959,23(2):151～156
[13] 兰州东风制药厂科技组.秦艽素注射液的制备及临床观察报告[J].中草药通讯,1973,(2):40～41
[14] 楼之岑,秦波.常用中药材品种整理和质量研究(北方编),第3册[M].北 京:北方医科大学·中国协和医科大学联合出版社,1996.374～416
[15] 杨肖锋,宋纯清.龙胆苦苷的肠内菌群代谢研究[J].中国中药杂志,2000,25(11),673-676
[16] 明·李时珍.本草纲目(校点本),上册[M].北京:人民卫生出版社,1982.783
[17] 明·刘文泰,等.本草晶汇精要,卷十北京:人民卫生出版社,1982.305
[18] 中国医科学院药物研究所。中草药有效成分研究,第一分册,第一版[M].北京:人民卫生出版社,1972.390
[19] 傅丰永,孙南君.秦艽化学成份的研究(Ⅰ)[J].药学学报,1958,6(4):198～203
[20] 梁晓天,于德泉,傅丰永.秦艽化学成分的研究Ⅱ.秦艽乙素的结构及其合成[J].药学学报,1964,11(6):412～415
[21] 薛智,梁晓天.秦艽丙素的结构[J]科学通报,1974,19(8):378～379
[22] Felicja Rulko, et al. Structure of alkaloid from Gentiana tibetica[J]. Rocz. chem.. 1967, 41 (3): 567
[23] Hisashi Kojima, Noriko Sato, Akiko Hatano, et al. Sterol Glucosides from Prunella vulgaris[J]. Phytochemistry, 1990, 29 (7): 2351～2355
[24] 钟静芬,李文兰,金育忠.表面活性剂在秦艽生物碱提取分离中的应用[J].甘肃医药.1992,11(5):292～294
[25] 康文艺,余正文.生物碱成分常用显色剂及一种检测内酰胺的特效方法[J].天然产物研究与开发,2002,14(3):39～41
[26] 章育中,王慕邹.中药秦艽中总生物碱的含量测定[J].药学学报,1962,9(2):71～75
[27] 王晓燕.秦艽及其混用晶中生物碱的含量测定[J]。中草药,1993,24(4):189～191
[2] 魏·吴晋等.神农本草经(重排本)[M].北京:人民卫生出版社,1982.67
[3] 粱·陶弘景.名医别录(辑校本)[M].北京:人民卫生出版社,1986.113
[4] 夏光成,萧培根,马毓泉.中药秦艽原植物的研究.药学学报,1965,12(6):399～411
[5] 刘艳红,李兴从,刘玉清,等.秦艽中的环烯醚萜甙成分[J].云南植物研究,1994,16(1):85～89
[6] 中国医科学院药物研究所.中草药有效成分研究(第一版),第一分册[M].北京:人民卫生出版社,1972.390
[7] Kubota T, Tomita Y. Derivation of gentianin from swertiamarin [J]. Tetrahedron Letters, 1961, 14: 453～454
[8] 林辉明.科植物基源生藥研究(第1報)中味成分Gentiopicroside定量[J].药学杂志(日),1976,96(3):356～361
[9] 郭亚健,陆蕴如.龙胆苦甙转化为秦艽丙素等生物碱的研究[J].药物分析杂志,1983,3(5):268～271
[10] 蔡宝蕴,穆芾芳,李文兰,等.秦艽生物碱提取新工艺[J].中草药,1986,17(3):15～16
[11] 王英,楼之岑.中药秦艽的研究概况[J].药学通报,1987,22(3):153～156
[12] 籍秀娟,刘耕陶,宋振玉.秦艽生物碱甲的药理作用Ⅱ.秦艽生物碱甲的抗炎作用及与一些临床有效药物的比较[J].生理学报,1959,23(2):151～156
[13] 兰州东风制药厂科技组.秦艽素注射液的制备及临床观察报告[J].中草药通讯,1973,(2):40～41
[14] 楼之岑,秦波.常用中药材品种整理和质量研究(北方编),第3册[M].北 京:北方医科大学·中国协和医科大学联合出版社,1996.374～416
[15] 杨肖锋,宋纯清.龙胆苦苷的肠内菌群代谢研究[J].中国中药杂志,2000,25(11),673-676
[16] 明·李时珍.本草纲目(校点本),上册[M].北京:人民卫生出版社,1982.783
[17] 明·刘文泰,等.本草晶汇精要,卷十北京:人民卫生出版社,1982.305
[18] 中国医科学院药物研究所。中草药有效成分研究,第一分册,第一版[M].北京:人民卫生出版社,1972.390
[19] 傅丰永,孙南君.秦艽化学成份的研究(Ⅰ)[J].药学学报,1958,6(4):198～203
[20] 梁晓天,于德泉,傅丰永.秦艽化学成分的研究Ⅱ.秦艽乙素的结构及其合成[J].药学学报,1964,11(6):412～415
[21] 薛智,梁晓天.秦艽丙素的结构[J]科学通报,1974,19(8):378～379
[22] Felicja Rulko, et al. Structure of alkaloid from Gentiana tibetica[J]. Rocz. chem.. 1967, 41 (3): 567
[23] Hisashi Kojima, Noriko Sato, Akiko Hatano, et al. Sterol Glucosides from Prunella vulgaris[J]. Phytochemistry, 1990, 29 (7): 2351～2355
[24] 钟静芬,李文兰,金育忠.表面活性剂在秦艽生物碱提取分离中的应用[J].甘肃医药.1992,11(5):292～294
[25] 康文艺,余正文.生物碱成分常用显色剂及一种检测内酰胺的特效方法[J].天然产物研究与开发,2002,14(3):39～41
[26] 章育中,王慕邹.中药秦艽中总生物碱的含量测定[J].药学学报,1962,9(2):71～75
[27] 王晓燕.秦艽及其混用晶中生物碱的含量测定[J]。中草药,1993,24(4):189～191