萝卜秦艽化学成分及质量控制研究
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摘要
萝卜秦艽为唇形科(Labiate)糙苏属(Phlomis Linn.)多年生草本植物萝卜秦艽Phlomis medicinalis Diels的干燥块根。主要分布于我国四川西部和西藏东部。该药性凉，味苦，具疏风清热、止咳化痰、生肌敛疮之功效，在西藏等地民间作为藏药螃蟹甲的代用品，用于治疗风热感冒、咳嗽痰多、疮疡久溃不敛等症，疗效显著。有关萝卜秦艽药材化学成分、药理药效及临床应用的研究资料较少，尚未见其质量标准控制方面的研究。本研究以萝卜秦艽为对象，对其化学成分和质量控制等方面进行了较为系统的研究，并就多个方面和螃蟹甲进行了比较分析，还对其生药学和药理药效进行了初步探讨，从而为其临床应用和进一步研究开发提供理论依据。本研究取得了如下进展：
1 对萝卜秦艽所含化学成分进行了较为系统的提取分离。从萝卜秦艽中共分离得到了34个化合物，鉴定出28个。其中环烯醚萜类成分7个、二萜类成分3个、有机酸及其酯类成分6个、糖类成分4个、甾体类成分2个、苯丙素类成分1个、三萜类成分1个、其它类成分4个。运用UV、IR、MS(FAB-MS、ESI-MS、EI-MS和HR-MS)、~1H-NMR、~(13)C-NMR、DEPT及2DNMR(HMBC和HMQC)等波谱分析技术结合理化性质对这些化合物的结构进行了鉴定，它们分别为phlomisoic acid(1)，phlomisoside Ⅴ(2)，phlomisoside Ⅲ(3)，三十烷酸(4)，三十烷酸对羟基苯乙酯(5)，邻苯二甲酸正丁异丁酯(6)，棕榈酸(7)，油酸(8)，β-谷甾醇(9)，胡萝卜苷(10)，5-羟基-7-甲氧基-4，6-二甲基-2-苯并呋喃酮(11)，4-羟甲基-2-糠醛(12)，1-去羟基山栀素甲酯(13)，山栀苷甲酯(14)，6-乙酰基山栀苷甲酯(15)，8-乙酰基山栀苷甲酯(16)，sesamoside(17)，phloyosideⅡ(18)和dehydropentstemoside(19)，notohamosin A(20)，acteoside(21)，3，4-二羟基苯乙醇(22)，琥珀酸(23)，蔗糖(24)，2，6-二聚果糖(25)，果糖丁苷(26)，D-葡萄糖(27)和D-果糖(28)。除化合物3外，其余所有化合物均为首次从该植物中分得，其中化合物4、5、6、11、15、20为首次从该属植物中分离得到，1为新天然产物，2、13为新化合物。
2 起草了萝卜秦艽药材的质量标准(草案)。从生药学方面，对萝卜秦艽性状、显微和薄层的鉴别进行了研究；采用RP-HPLC法，以sesamoside、山栀苷甲酯、dehydropentstemoside和8-乙酰基山栀苷甲酯为指标，对萝卜秦艽中含量
Luoboqinjiao is the dried root of perennial herbage Phlomis medicinalis Diels which belongs to the genus Phlomis of family Labiate. It distributes in the west of Sichuan province and east of Xizang province in southwest China. According to the theories of Traditional Tibetan Medicine, it is cool in property and bitter in taste, and it has the functions of dispelling wind and clearing heat, relieving cough and reducing phlegm, promoting tissue regeneration and wound healing, and it is used as Tibetan Materia Medicine RADIX PHLOMII for symptoms and signs of common cold due to wind heat, cough with profuse sputum, pyogenic skin infection without healing for a long time, etc. Since there is little information about this crude drug as so far, its quality control items can't be established at present time. In order to study and develop Luoboqinjiao to provide theoretical proof and practical reference for clinical application, and to expatiate Luoboqinjiao used as Pangxiejia in various aspects, Luoboqinjiao was selected as the research object. Luoboqinjiao was studied systematically on the chemical constituents and quality control, and compared with Pangxiejia in various aspects, and approached simply on pharmacognosy and pharmacology at the same time. Our research results are as follows:
1 To studies on chemical constituents from the roots of Luoboqinjiao. thirty-four compounds were isolated and repeatedly purified from 95% EtOH extracts of the roots of Luoboqinjiao and twenty-eight of them were identified by physicochemical properties and spectral analysis of UV, IR, MS(FAB-MS, ESI-MS, EI-MS and HR-MS), NMR(~1H-NMR and ~(13)C-NMR), DEPT and 2DNMR(HSQC and HMBC). These compounds were identified as follows: phlomisoic acid(1), phlomisoside V(2), phlomisoside III(3), triacontanoic acid(4), triacontanoic acid, 2-(4-hydroxyphenyl)ethyl ester(5), phthalic acid, butyl isobutyl ester(6), palmitic acid(7), oleic acid(8), β-sitosterol(9), daucosterol(10), 5-hydroxy-7-methoxy-4,6-dimethylphthalide( 11 ),4-hydroxymethyl-2-furaldehyde( 12), 1 -dehydroxyshanzhigenin methyl ester(13), shanzhiside methyl ester(14), 6-O-acetyl-shanzhiside methyl ester(15), 8-O-acetyl-shanzhiside methyl ester(16), sesamoside(17), phloyoside II(18),
1 对萝卜秦艽所含化学成分进行了较为系统的提取分离。从萝卜秦艽中共分离得到了34个化合物，鉴定出28个。其中环烯醚萜类成分7个、二萜类成分3个、有机酸及其酯类成分6个、糖类成分4个、甾体类成分2个、苯丙素类成分1个、三萜类成分1个、其它类成分4个。运用UV、IR、MS(FAB-MS、ESI-MS、EI-MS和HR-MS)、~1H-NMR、~(13)C-NMR、DEPT及2DNMR(HMBC和HMQC)等波谱分析技术结合理化性质对这些化合物的结构进行了鉴定，它们分别为phlomisoic acid(1)，phlomisoside Ⅴ(2)，phlomisoside Ⅲ(3)，三十烷酸(4)，三十烷酸对羟基苯乙酯(5)，邻苯二甲酸正丁异丁酯(6)，棕榈酸(7)，油酸(8)，β-谷甾醇(9)，胡萝卜苷(10)，5-羟基-7-甲氧基-4，6-二甲基-2-苯并呋喃酮(11)，4-羟甲基-2-糠醛(12)，1-去羟基山栀素甲酯(13)，山栀苷甲酯(14)，6-乙酰基山栀苷甲酯(15)，8-乙酰基山栀苷甲酯(16)，sesamoside(17)，phloyosideⅡ(18)和dehydropentstemoside(19)，notohamosin A(20)，acteoside(21)，3，4-二羟基苯乙醇(22)，琥珀酸(23)，蔗糖(24)，2，6-二聚果糖(25)，果糖丁苷(26)，D-葡萄糖(27)和D-果糖(28)。除化合物3外，其余所有化合物均为首次从该植物中分得，其中化合物4、5、6、11、15、20为首次从该属植物中分离得到，1为新天然产物，2、13为新化合物。
2 起草了萝卜秦艽药材的质量标准(草案)。从生药学方面，对萝卜秦艽性状、显微和薄层的鉴别进行了研究；采用RP-HPLC法，以sesamoside、山栀苷甲酯、dehydropentstemoside和8-乙酰基山栀苷甲酯为指标，对萝卜秦艽中含量
Luoboqinjiao is the dried root of perennial herbage Phlomis medicinalis Diels which belongs to the genus Phlomis of family Labiate. It distributes in the west of Sichuan province and east of Xizang province in southwest China. According to the theories of Traditional Tibetan Medicine, it is cool in property and bitter in taste, and it has the functions of dispelling wind and clearing heat, relieving cough and reducing phlegm, promoting tissue regeneration and wound healing, and it is used as Tibetan Materia Medicine RADIX PHLOMII for symptoms and signs of common cold due to wind heat, cough with profuse sputum, pyogenic skin infection without healing for a long time, etc. Since there is little information about this crude drug as so far, its quality control items can't be established at present time. In order to study and develop Luoboqinjiao to provide theoretical proof and practical reference for clinical application, and to expatiate Luoboqinjiao used as Pangxiejia in various aspects, Luoboqinjiao was selected as the research object. Luoboqinjiao was studied systematically on the chemical constituents and quality control, and compared with Pangxiejia in various aspects, and approached simply on pharmacognosy and pharmacology at the same time. Our research results are as follows:
1 To studies on chemical constituents from the roots of Luoboqinjiao. thirty-four compounds were isolated and repeatedly purified from 95% EtOH extracts of the roots of Luoboqinjiao and twenty-eight of them were identified by physicochemical properties and spectral analysis of UV, IR, MS(FAB-MS, ESI-MS, EI-MS and HR-MS), NMR(~1H-NMR and ~(13)C-NMR), DEPT and 2DNMR(HSQC and HMBC). These compounds were identified as follows: phlomisoic acid(1), phlomisoside V(2), phlomisoside III(3), triacontanoic acid(4), triacontanoic acid, 2-(4-hydroxyphenyl)ethyl ester(5), phthalic acid, butyl isobutyl ester(6), palmitic acid(7), oleic acid(8), β-sitosterol(9), daucosterol(10), 5-hydroxy-7-methoxy-4,6-dimethylphthalide( 11 ),4-hydroxymethyl-2-furaldehyde( 12), 1 -dehydroxyshanzhigenin methyl ester(13), shanzhiside methyl ester(14), 6-O-acetyl-shanzhiside methyl ester(15), 8-O-acetyl-shanzhiside methyl ester(16), sesamoside(17), phloyoside II(18),
引文
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