草麻黄表观型化学组成特征研究柳叶白前化学成分的研究
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摘要
草麻黄(Ephedra sinica Stapf)为麻黄科麻黄属植物,柳叶白前(Cynanchum stauntonii (Decne) Schltr. ex Levl.)为萝藦科鹅绒藤属植物,二者分别是中国药典收载的中药麻黄的基源植物之一和中药白前的基源植物之一。草麻黄主要含苯丙胺类生物碱、黄酮类以及酚酸类成分,柳叶白前主要含C21型甾体苷类成分。鉴于天然存在的苯丙胺类生物碱、黄酮类成分以及C21甾体及其苷类成分均具有结构的多样性和特征性,并具有广泛的药理作用,为了从天然有机化学的角度深入研究天然药物的组成特征以及这种组成特征在药用植物基源鉴定方面的应用,本论文分别对具有化学组成特征的草麻黄和柳叶白前的正丁醇萃取部位进行了系统的化学成分研究。
本论文运用多种色谱方法和波谱技术,对上述两种植物进行了系统的化学成分研究。从草麻黄85%乙醇提取物中分离并鉴定了58个化合物(1*-58),发现新化合物8个(1*-8*)。化合物编号和名称见Table1,结构见Figure1。其中新化合物包括苯丙胺类生物碱1*,香豆素衍生物2*以及芳香酸衍生物3*,化合物4*-8*为新的酰胺类化合物,新化合物5*-8*为四对旋转异构体；从柳叶白前95%乙乙醇提取物的正丁醇部位的大孔树脂60%洗脱部位分离得到20个化合物,鉴定出其中的16个,发现新化合物5个(1*-5*)。化合物编号和名称见Table1,结构见Figure1。其中包括两个新的C21甾体类化合物(1*和2*),两个新的C21甾苷类成分(3*和4*)以及一个新的木脂素类成分(5*)。
对缺少植物形态学和组织学鉴别特征的中药及其制成品的基源鉴定和质量控制研究一直是中药研究中具有挑战性的研究内容。通过采用植物化学的研究方法表达中药化学组成的整体特征,最终达到中药及其制成品的基源鉴定的目的已经成为该研究领域的共识。本论文在对草麻黄化学成分研究的基础上,采用规范化的程序进一步探讨了来源于两个不同种麻黄,草麻黄(E. sinica Stapf)和中麻黄(E.intermedia Schrenk et C.A. Mey.)的6个样品的专属性特征对照物质(extract-P部分)的1HNMR和HPLC指纹分析方法。通过将各单体成分与各不同来源样品的1HNMR口HPLC图谱进行比较,完成了两个种麻黄的1HNMR和HPLC指纹图谱特征性信号的解析。结果表明两个种的麻黄均主要显示麻黄中具有结构特征性化学成分-苯丙胺类生物碱的特征共振信号(1HNNR谱上并未显示黄酮类成分的特征共振信号),既具有一致性也有不同之处。通过HPLC和HPLC-MS在线分析的方法对extract-P的化学成分特征进行了进一步的确证。所得的1HNMR谱特征信号和HPLC峰均可明确归属为相应的单体化合物。1HNMR谱结合HPLC色谱峰所提供的特征化合物的结构和成分信息,可用于麻黄属植物的基源鉴定。
Ephedra sinica Stapf belonging to the family of Ephedraceae,and Cynachum stauntonii (Decne.)Schltr. ex Levl., a perennial medicinal herb from the family of Asclepiadaceae, have been used as original plants of Eephedrae Herba and Cynanchi stauntonii Rhizoma Et Radix, respectively, in Chinese pharmacopoeia (2010). It has been reported that phenylalkylamines alkaloids, flavonoids and phenolic compounds were the main constituents from the stems of E. sinica, and C21steroids were the main constituents from the roots of C. stauntonii. Based on the diverse structures and extensive pharmacological effects of these types of compounds, this thesis studied the chemical constituents of the stems of E. sinica and the roots of C. stautonii, expecting to find more active substance and functions of the natural medicine.
By using a variety of chromatographic techniques and spectroscopic methods,58compounds (1*-58) were isolated and structurally determined from the85%EtOH extract of the stems of E. sinica. Names and structures of the purified compounds are listed in Table1and Figure1, respectively. Among them, compounds1*-8*are novel compounds, compound1*is a new phenylalkylamines alkaloids, compound2*is a new coumarin, compound3*is a new phenolic compound, compounds4*-8*are new amides glycosides, among them5*-8*are four pairs of rotational isomers. From the n-BuOH fraction of95%EtOH extract of the roots of C. stauntonii, isolated20compouds,16of them were elucidated. Of which,5are new compounds (1*-5*),1*and2*are new steroids,3*and4*are new steroidal glycosides and5*is a new lignans. Names and structures of the purified compounds are listed in Table2and Figure2, respectively.
The original determination of plant-derived subjects in the system of traditional herbal medicines is often complicated by the lack of morphological features in visual or microscopic inspection. Improved methods are urgently needed. In this paper, the profiles of proton nuclear magnetic resonance (1H NMR) and high performance liquid chromatography (HPLC) of fractionated polar extracts from samples of E. sinica and E. intermedia were recorded and analyzed by comparing them to each other and to those of the compounds isolated in this work. The1H NMR spectra revealed not only the common features of chemical composition among collected samples of Epheda species with the characteristic signals of their major constituents, phenylalkylamines alkaloids, being exhibited explicitly and reproducibly, but also the significantly signature features in the composition of signals when compared to other species. These features were further confirmed by HPLC and online HPLC-MS (mass spectrometry) analyses. On the basis of chemical investigation, the signals and peaks in the profiles of1H NMR and HPLC were unambiguously assigned to their corresponding monomers. The general feature of1H NMR spectrum coupled with that of HPLC profile established for authentic sample explicitly provided the data of structures and composition for those particular compounds, which can be used as signature features for original authentication of Ephedra species.
本论文运用多种色谱方法和波谱技术,对上述两种植物进行了系统的化学成分研究。从草麻黄85%乙醇提取物中分离并鉴定了58个化合物(1*-58),发现新化合物8个(1*-8*)。化合物编号和名称见Table1,结构见Figure1。其中新化合物包括苯丙胺类生物碱1*,香豆素衍生物2*以及芳香酸衍生物3*,化合物4*-8*为新的酰胺类化合物,新化合物5*-8*为四对旋转异构体；从柳叶白前95%乙乙醇提取物的正丁醇部位的大孔树脂60%洗脱部位分离得到20个化合物,鉴定出其中的16个,发现新化合物5个(1*-5*)。化合物编号和名称见Table1,结构见Figure1。其中包括两个新的C21甾体类化合物(1*和2*),两个新的C21甾苷类成分(3*和4*)以及一个新的木脂素类成分(5*)。
对缺少植物形态学和组织学鉴别特征的中药及其制成品的基源鉴定和质量控制研究一直是中药研究中具有挑战性的研究内容。通过采用植物化学的研究方法表达中药化学组成的整体特征,最终达到中药及其制成品的基源鉴定的目的已经成为该研究领域的共识。本论文在对草麻黄化学成分研究的基础上,采用规范化的程序进一步探讨了来源于两个不同种麻黄,草麻黄(E. sinica Stapf)和中麻黄(E.intermedia Schrenk et C.A. Mey.)的6个样品的专属性特征对照物质(extract-P部分)的1HNMR和HPLC指纹分析方法。通过将各单体成分与各不同来源样品的1HNMR口HPLC图谱进行比较,完成了两个种麻黄的1HNMR和HPLC指纹图谱特征性信号的解析。结果表明两个种的麻黄均主要显示麻黄中具有结构特征性化学成分-苯丙胺类生物碱的特征共振信号(1HNNR谱上并未显示黄酮类成分的特征共振信号),既具有一致性也有不同之处。通过HPLC和HPLC-MS在线分析的方法对extract-P的化学成分特征进行了进一步的确证。所得的1HNMR谱特征信号和HPLC峰均可明确归属为相应的单体化合物。1HNMR谱结合HPLC色谱峰所提供的特征化合物的结构和成分信息,可用于麻黄属植物的基源鉴定。
Ephedra sinica Stapf belonging to the family of Ephedraceae,and Cynachum stauntonii (Decne.)Schltr. ex Levl., a perennial medicinal herb from the family of Asclepiadaceae, have been used as original plants of Eephedrae Herba and Cynanchi stauntonii Rhizoma Et Radix, respectively, in Chinese pharmacopoeia (2010). It has been reported that phenylalkylamines alkaloids, flavonoids and phenolic compounds were the main constituents from the stems of E. sinica, and C21steroids were the main constituents from the roots of C. stauntonii. Based on the diverse structures and extensive pharmacological effects of these types of compounds, this thesis studied the chemical constituents of the stems of E. sinica and the roots of C. stautonii, expecting to find more active substance and functions of the natural medicine.
By using a variety of chromatographic techniques and spectroscopic methods,58compounds (1*-58) were isolated and structurally determined from the85%EtOH extract of the stems of E. sinica. Names and structures of the purified compounds are listed in Table1and Figure1, respectively. Among them, compounds1*-8*are novel compounds, compound1*is a new phenylalkylamines alkaloids, compound2*is a new coumarin, compound3*is a new phenolic compound, compounds4*-8*are new amides glycosides, among them5*-8*are four pairs of rotational isomers. From the n-BuOH fraction of95%EtOH extract of the roots of C. stauntonii, isolated20compouds,16of them were elucidated. Of which,5are new compounds (1*-5*),1*and2*are new steroids,3*and4*are new steroidal glycosides and5*is a new lignans. Names and structures of the purified compounds are listed in Table2and Figure2, respectively.
The original determination of plant-derived subjects in the system of traditional herbal medicines is often complicated by the lack of morphological features in visual or microscopic inspection. Improved methods are urgently needed. In this paper, the profiles of proton nuclear magnetic resonance (1H NMR) and high performance liquid chromatography (HPLC) of fractionated polar extracts from samples of E. sinica and E. intermedia were recorded and analyzed by comparing them to each other and to those of the compounds isolated in this work. The1H NMR spectra revealed not only the common features of chemical composition among collected samples of Epheda species with the characteristic signals of their major constituents, phenylalkylamines alkaloids, being exhibited explicitly and reproducibly, but also the significantly signature features in the composition of signals when compared to other species. These features were further confirmed by HPLC and online HPLC-MS (mass spectrometry) analyses. On the basis of chemical investigation, the signals and peaks in the profiles of1H NMR and HPLC were unambiguously assigned to their corresponding monomers. The general feature of1H NMR spectrum coupled with that of HPLC profile established for authentic sample explicitly provided the data of structures and composition for those particular compounds, which can be used as signature features for original authentication of Ephedra species.
引文
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