蜘蛛香炮制前后的物质基础研究
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摘要
本论文主要对蜘蛛香(Valeriana jatamansi Jones)根的化学成分进行了研究,并利用HPLC分析,比较蜘蛛香炮制前后化学成分的变化,初步探讨了蜘蛛香炮制的工艺。
利用现代天然产物化学方法和技术,如硅胶柱层析、ODS反相柱色谱、薄层色谱、Sephadex LH-20凝胶柱、MCI柱、HPLC高效液相色谱仪等从蜘蛛香中分离出22个化合物。综合运用1D、2D-NMR和质谱(MS)等多种现代波谱学技术鉴定了化合物的结构,包括2个新的化合物和1个新的天然产物,其中1个为高度氧化的环烯醚萜,另外2个是含氯的酰化的环烯醚萜,已知的化合物的结构类型涉及环烯醚萜、倍半萜、木脂素、甾体等。
蜘蛛香系败酱科(Valerianaceae)缬草属(Valeriana)植物,多年生草本,分布在中国和印度等地,在中国具有悠久的应用历史。本论文对产自云南的蜘蛛香的根及根茎进行了化学成分研究,从其95%的乙醇提取物中分离出22个化合物,包括3个新的化合物,命名为jatamanin N (1)、jatamanin O (2)和jatamanin P (3)。已知的化合物分别为(3S,4R,5S,7S,8S,9S)-3,8-epoxy-7-hydroxy-4,8-dimethylperhydrocyclopent-a[c]pyran (4), (3S,4S,5S,7S,8S,9S)-3,8-ethoxy-7-hydroxy-4,8-dimethylperhydrocyclop-enta[c]pyran (5),4-β-hydroxy-8-β-methoxy-10-methylene-2,9-dioxatricyclo[4.3.1.03.7]de-can (6),6-hydroxy-7-(hydroxymethyl)-4-methylenehexahydrocyclopenta[c]pyran-1-(3H)o-ne (7), jatamansi A (8), jatamansi G (9), volvatrate A (10),8-hydroxypinoresinol (11), 2,5-di(4-hydroxy-3-methoxyphenyl)-1,4-dioxan (12), pinoresinol (13), (+)-2-(3,4-dime-thoxyphenyl)-6-(3,4-dihydroxyphenyl)-2,7-dioxabicyclo[3,3,0]octane (14), pinoresinol monomethyl ether (15), prinsepoil (16), (-)-massoniresinol (17), cinnamolide (18), valeriananoid A (19), valeriananoid C (20),β-sitoserol(21)和cholest-5-en-3β-ol (22)。
缬草具有抗抑郁活性,在欧洲被广泛用于镇静催眠,其主要的活性成分是缬草素类化合物,在国内则采用炮制后的蜘蛛香用药,主要用于健胃消食等。蜘蛛香生品的化学成分也具有缬草素类化合物,但因缬草素类性质不稳定,易分解,炮制后的化学成分会发生不同程度的改变。本论文采用烘箱加热的方式,代替蜘蛛香的传统炮制方法,再运用高效液相色谱技术对烘烤炮制前后的蜘蛛香的化学成分含量变化进行分析。结果表明,150℃烘烤10 mmin后,各成分的含量没有明显变化,20 min后HPLC图谱分析缬草醛含量开始增加,30 min后的缬草素含量明显降低,而缬草醛的含量明显增加。
This dissertation mainly reported the investigation on the chemical constituents in the roots and rhizomes of Chinese medicinal plant Valeriana jatamansi Jones. In addition, the chemical components of V. jatamansi after processing were compared on the basis of HPLC analysis.
Totally 22 compounds were isolated and identified from the roots of V. jatamansi by several isolation and purification methods, such as silica gel column chromatography, MCI, Sephadex LH-10, ODS and HPLC,Their chemical structures were elucidated on the basis spectral data together with phytochemical analysis. Among them, two compounds were new ones and one compound was new natural product. The types of the compounds included iridoids, lignans, sesquiterpenoids and steroids.
V. jatamansi Jones, a perennial herb plant, belongs to the genus Valeriana (Valerianaceae). It is mainly distributed in the southwest of China and India, and was utilized as a Chinese folk medicine in long history. Our investigation on the chemical constituents of the roots and rhizomes of this plant collected in Yunnan province resulted in the isolation of 22 compounds, including three new ones. The new compounds were identified as jatamanin N (1)、jatamanin O (2), and jatamanin P (3), the basis of spectroscopic methods. Others known compounds were identified as (3S,4R,5S,7S,8S, 9S)-3,8-epoxy-7-hydroxy-4,8-dimethylperhydrocyclopenta[c]pyran (4), (3S,4S,5S,7S,8S, 9S)-3,8-ethoxy-7-hydroxy-4,8-dimethylperhydrocyclopenta[c]pyran (5),4-β-hydroxy-8-β-methoxy-10-methylene-2,9-dioxatricyclo[4.3.1.03.7] decan (6),6-hydroxy-7-(hydroxyl-methyl)-4-methyl-enehexahydrocyclopenta[c]pyran-1-(3H)-one (7), jatamansi A (8), jatamansi G (9), volvatrate A (10),8-hydroxypinoresinol (11),2,5-di(4-hydroxy-3-methoxyphenyl)-1,4-dioxan (12), pinoresinol (13), (+)-2-(3,4-dimethoxyphenyl)-6-(3,4-dihydroxyphenyl)-2,7-dioxabicyclo[3,3,0]octane (14), pinoresinol monomethyl ether (15), prinsepoil (16), (-)-massoniresinol (17), cinnamolide (18), valeriananoid A (19), valeriananoid C (20),β-sitoserol(21) and cholest-5-en-3p-ol (22).
The roots and rhizomes of some Valeriana species have been used in traditional medicine as a sedative for centuries. V. jatamansi has been utilizing as folk drug in China for a long time, and modern pharmacological studies have proved that it possesses sedative, hypnic, antidepressive, antibacterial and antiviral activities, and in Chinese traditional medicine, the processed product of V. jatamansi was used for invigorating stomach and promoting digestion.
Chemical investigations of Valeriana species have mainly focused on low-polarity components, leading to the isolation of two major groups of constituents:essential oil sesquiterpenes and valepotriates. The chemical constituents of V. jatamansi will change because valtrates in it are not stable and easy to decompose. In this thesis, the traditional processing method was instead by heating with oven at 150℃, and then we analyzed the changes in contents of the samples with and without processing by HPLC. Consequently, the contents didn't show significant change after baking for 10 minutes; the content of baldrinals began to increase after 20 minutes; and the content of valtrates decreased significantly, whereas, the content of baldrinals increased significantly after 30 minutes.
利用现代天然产物化学方法和技术,如硅胶柱层析、ODS反相柱色谱、薄层色谱、Sephadex LH-20凝胶柱、MCI柱、HPLC高效液相色谱仪等从蜘蛛香中分离出22个化合物。综合运用1D、2D-NMR和质谱(MS)等多种现代波谱学技术鉴定了化合物的结构,包括2个新的化合物和1个新的天然产物,其中1个为高度氧化的环烯醚萜,另外2个是含氯的酰化的环烯醚萜,已知的化合物的结构类型涉及环烯醚萜、倍半萜、木脂素、甾体等。
蜘蛛香系败酱科(Valerianaceae)缬草属(Valeriana)植物,多年生草本,分布在中国和印度等地,在中国具有悠久的应用历史。本论文对产自云南的蜘蛛香的根及根茎进行了化学成分研究,从其95%的乙醇提取物中分离出22个化合物,包括3个新的化合物,命名为jatamanin N (1)、jatamanin O (2)和jatamanin P (3)。已知的化合物分别为(3S,4R,5S,7S,8S,9S)-3,8-epoxy-7-hydroxy-4,8-dimethylperhydrocyclopent-a[c]pyran (4), (3S,4S,5S,7S,8S,9S)-3,8-ethoxy-7-hydroxy-4,8-dimethylperhydrocyclop-enta[c]pyran (5),4-β-hydroxy-8-β-methoxy-10-methylene-2,9-dioxatricyclo[4.3.1.03.7]de-can (6),6-hydroxy-7-(hydroxymethyl)-4-methylenehexahydrocyclopenta[c]pyran-1-(3H)o-ne (7), jatamansi A (8), jatamansi G (9), volvatrate A (10),8-hydroxypinoresinol (11), 2,5-di(4-hydroxy-3-methoxyphenyl)-1,4-dioxan (12), pinoresinol (13), (+)-2-(3,4-dime-thoxyphenyl)-6-(3,4-dihydroxyphenyl)-2,7-dioxabicyclo[3,3,0]octane (14), pinoresinol monomethyl ether (15), prinsepoil (16), (-)-massoniresinol (17), cinnamolide (18), valeriananoid A (19), valeriananoid C (20),β-sitoserol(21)和cholest-5-en-3β-ol (22)。
缬草具有抗抑郁活性,在欧洲被广泛用于镇静催眠,其主要的活性成分是缬草素类化合物,在国内则采用炮制后的蜘蛛香用药,主要用于健胃消食等。蜘蛛香生品的化学成分也具有缬草素类化合物,但因缬草素类性质不稳定,易分解,炮制后的化学成分会发生不同程度的改变。本论文采用烘箱加热的方式,代替蜘蛛香的传统炮制方法,再运用高效液相色谱技术对烘烤炮制前后的蜘蛛香的化学成分含量变化进行分析。结果表明,150℃烘烤10 mmin后,各成分的含量没有明显变化,20 min后HPLC图谱分析缬草醛含量开始增加,30 min后的缬草素含量明显降低,而缬草醛的含量明显增加。
This dissertation mainly reported the investigation on the chemical constituents in the roots and rhizomes of Chinese medicinal plant Valeriana jatamansi Jones. In addition, the chemical components of V. jatamansi after processing were compared on the basis of HPLC analysis.
Totally 22 compounds were isolated and identified from the roots of V. jatamansi by several isolation and purification methods, such as silica gel column chromatography, MCI, Sephadex LH-10, ODS and HPLC,Their chemical structures were elucidated on the basis spectral data together with phytochemical analysis. Among them, two compounds were new ones and one compound was new natural product. The types of the compounds included iridoids, lignans, sesquiterpenoids and steroids.
V. jatamansi Jones, a perennial herb plant, belongs to the genus Valeriana (Valerianaceae). It is mainly distributed in the southwest of China and India, and was utilized as a Chinese folk medicine in long history. Our investigation on the chemical constituents of the roots and rhizomes of this plant collected in Yunnan province resulted in the isolation of 22 compounds, including three new ones. The new compounds were identified as jatamanin N (1)、jatamanin O (2), and jatamanin P (3), the basis of spectroscopic methods. Others known compounds were identified as (3S,4R,5S,7S,8S, 9S)-3,8-epoxy-7-hydroxy-4,8-dimethylperhydrocyclopenta[c]pyran (4), (3S,4S,5S,7S,8S, 9S)-3,8-ethoxy-7-hydroxy-4,8-dimethylperhydrocyclopenta[c]pyran (5),4-β-hydroxy-8-β-methoxy-10-methylene-2,9-dioxatricyclo[4.3.1.03.7] decan (6),6-hydroxy-7-(hydroxyl-methyl)-4-methyl-enehexahydrocyclopenta[c]pyran-1-(3H)-one (7), jatamansi A (8), jatamansi G (9), volvatrate A (10),8-hydroxypinoresinol (11),2,5-di(4-hydroxy-3-methoxyphenyl)-1,4-dioxan (12), pinoresinol (13), (+)-2-(3,4-dimethoxyphenyl)-6-(3,4-dihydroxyphenyl)-2,7-dioxabicyclo[3,3,0]octane (14), pinoresinol monomethyl ether (15), prinsepoil (16), (-)-massoniresinol (17), cinnamolide (18), valeriananoid A (19), valeriananoid C (20),β-sitoserol(21) and cholest-5-en-3p-ol (22).
The roots and rhizomes of some Valeriana species have been used in traditional medicine as a sedative for centuries. V. jatamansi has been utilizing as folk drug in China for a long time, and modern pharmacological studies have proved that it possesses sedative, hypnic, antidepressive, antibacterial and antiviral activities, and in Chinese traditional medicine, the processed product of V. jatamansi was used for invigorating stomach and promoting digestion.
Chemical investigations of Valeriana species have mainly focused on low-polarity components, leading to the isolation of two major groups of constituents:essential oil sesquiterpenes and valepotriates. The chemical constituents of V. jatamansi will change because valtrates in it are not stable and easy to decompose. In this thesis, the traditional processing method was instead by heating with oven at 150℃, and then we analyzed the changes in contents of the samples with and without processing by HPLC. Consequently, the contents didn't show significant change after baking for 10 minutes; the content of baldrinals began to increase after 20 minutes; and the content of valtrates decreased significantly, whereas, the content of baldrinals increased significantly after 30 minutes.
引文
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