贝母类药材的红外光谱分析与鉴定
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摘要
贝母Bulbus·Fritillaria为百合科Liliaceae贝母属Fritillaria L.植物的干燥鳞茎,是常见的中药材之一。贝母在我国有2000多年悠久的使用历史,早在汉代的《神农本草经》就有记载,被列入中品,它有清热润肺,化痰止咳之功效,主治肺热燥咳、咯痰带血、痰多胸闷等症。
由于与贝母同属的贝母属植物品种繁多,极易混淆,且不同部位及不同产地的贝母其化学成分各有差异,影响药理效应。所以迫切需要建立快速、准确的鉴别方法。红外光谱法是鉴别化合物和确定物质结构的常用手段之一。中药材的红外光谱图是其所含各成分的叠加谱,反映了中药材整体质量信息。
本论文采用红外光谱三级宏观指纹鉴定法结合计算机分析比对软件等技术对中药贝母的质量进行了初步的分析与鉴定。主要研究成果有：(1)不同产地野生的川贝和平贝之间存在着较大差异,造成这种差异的原因是它们的气候条件、地形地貌、土壤等生长条件相差较大,因而引起所含化学成分含量差异较大。同一省内的非常相似,但也不完全相同。可见,产地不同对贝母化学成分的种类影响不大,但含量积累的影响较大。(2)不同种属贝母原药材粉末的一级鉴定中,川贝和浙贝在1647cm-1具有明显的特征峰,其它三种贝母的特征峰则在1654cm-1。在二级导数谱中,川贝在1647cm-1的谱峰最强,浙贝则变成1640cm-1和1628cm-1双峰,其它三种贝母基本一致都在1638cm-1和1627cm-1两处出峰。在二维相关谱的1200～1300cm-1波段范围内,有3个比较明显的自动峰,对应着贝母中=C-O-C-的特征振动,它们的交叉峰均为正。(3)对松贝、青贝和炉贝三种川贝母的心芽、鳞叶和整体鳞茎研究显示,松贝的心芽和鳞叶含有的有效成分明显不同于青贝和炉贝,心芽中同样含有淀粉和有效成分,因此这与药典中规定的,松贝、青贝和炉贝在入药时,并未除去心芽,还是相吻合的,同时还证明了松贝的质量明显好于后两者。(4)经水和甲醇提取后,原药材提取物中总生物碱和总皂苷等有效成分的相对含量得到了富集。川贝与其他几种贝母的水提物与醇提物的红外光谱中1100cm-1与1630cm-1附近的相对峰强度明显不同,这也与传统观念所认为的川贝的药效优于其他品种贝母的观点相一致。研究中还发现贝母水提物的红外光谱中有1120±5、618cm-1等硫酸盐的特征吸收峰,这与其加工过程中使用硫磺熏蒸等处理有关,说明通过红外光谱还可以对贝母中的硫残留进行检测。
综上所述,红外光谱三级宏观指纹鉴定技术结合计算机比对软件技术在中药质量控制中具有良好的应用前景。
Bulbus Fritillariae (in Chinese named Beimu), referred to the bulbs of several Fritillaria species (Liliaceae), is a commonly used anti-tussive and expectorant herb in traditional Chinese medicine (TCM) for more than 2000 years which is also used as a dietary supplement in China.
Because there are many varieties of herbal medicine, which are the same as Beimu belong to Fritillaria, they are quite similar, and different parts and producing areas of Beimu have diverse chemical constituents and drug effects. Therefore, rapid and accurate identification method can play a significant role on guaranteeing their curative effect. Infrared spectroscopy (IR) is one of the routine means to distinguish chemical compounds and confirm material structures. The IR spectra of Traditional Chinese Medicine (TCM) include spectra of each compound in the system, which shows the whole information of TCM.
In this thesis, we have analyzed and identified the quality of Beimu via the multi-steps IR macro-fingerprint method and combined with the software of Computer Analysis Comparison. The main conclusions include:(1) Feral Bulbus Fritillariae Cirrhosae(CB) and feral Bulbus Fritillariae Ussuriensis(UB) of different origins are quite different, the reason of which is that they have quite different grown conditions of climatic conditions, topography, soil and so on. So, these distinction leads to the content of their chemical components. Beimu in the same province are quite similar but not the same. It is thus clear that the influence of the kind of Beimu chemical components by the different origins is not so big while it is big in the content accumulation. (2) The IR spectra of the different kinds of Beimu materials shows that CB and Bulbus Fritillariae Thunbergii (TB) both have a obvious peak at 1647 cm-1 while the peak of other three Beimu is at 1654 cm-1. In the second derivative IR spectra, CB has the strongest peak at 1647 cm-1, TB changed into two peaks at 1640 cm-1 and 1628 cm-1, while other three Beimu are quite similar at 1638cm-1 and 1627cm-1. The three peaks characteristic intensity in the region at 1200-1300cm-1 of the 2D-IR spectra correspond the stretching of the -C-O-C-groups. (3) The research of three different CB:Songbei(SB), Qingbei(QB), Lubei(LB) shows that the different parts of the bulbs contains different active principle. The bud and scale leaf of SB contain dissimilitude active principle with QB and LB. The bud also contains the same starch and active principle with the bulb. So, this is consistent with the rules of pharmacopeia that not remove the bud of CB when using them. Meanwhile, it is also identified that the quality of SB is much better than the other two. (4) The starch contained in the original medicinal extracts has greatly reduced, while the relative content of the effective components, such as the total alkaloid and saponins, has increased. The IR spectrums of the aqueous and alcohol extract of F. cirrhosae are distinctly different with the relatively peak intensity with the other Beimu at 1100cm-1 and 1630cm-1. And We can find peaks at 1120±5 and 618cm-1 in the IR spectrum of Beimu aqueous extract which are the characteristic absorption peaks of the sulfate, and this is related to the use of sulfur fumigation in the processing. And it is also show that the sulphur residue in Beimu can be identified by the FTIR.
In a word, the multi-steps IR Macro-Fingerprint method and combined with the software of Computer Analysis Comparison have great applying foreground in the quality control of TCM area.
由于与贝母同属的贝母属植物品种繁多,极易混淆,且不同部位及不同产地的贝母其化学成分各有差异,影响药理效应。所以迫切需要建立快速、准确的鉴别方法。红外光谱法是鉴别化合物和确定物质结构的常用手段之一。中药材的红外光谱图是其所含各成分的叠加谱,反映了中药材整体质量信息。
本论文采用红外光谱三级宏观指纹鉴定法结合计算机分析比对软件等技术对中药贝母的质量进行了初步的分析与鉴定。主要研究成果有：(1)不同产地野生的川贝和平贝之间存在着较大差异,造成这种差异的原因是它们的气候条件、地形地貌、土壤等生长条件相差较大,因而引起所含化学成分含量差异较大。同一省内的非常相似,但也不完全相同。可见,产地不同对贝母化学成分的种类影响不大,但含量积累的影响较大。(2)不同种属贝母原药材粉末的一级鉴定中,川贝和浙贝在1647cm-1具有明显的特征峰,其它三种贝母的特征峰则在1654cm-1。在二级导数谱中,川贝在1647cm-1的谱峰最强,浙贝则变成1640cm-1和1628cm-1双峰,其它三种贝母基本一致都在1638cm-1和1627cm-1两处出峰。在二维相关谱的1200～1300cm-1波段范围内,有3个比较明显的自动峰,对应着贝母中=C-O-C-的特征振动,它们的交叉峰均为正。(3)对松贝、青贝和炉贝三种川贝母的心芽、鳞叶和整体鳞茎研究显示,松贝的心芽和鳞叶含有的有效成分明显不同于青贝和炉贝,心芽中同样含有淀粉和有效成分,因此这与药典中规定的,松贝、青贝和炉贝在入药时,并未除去心芽,还是相吻合的,同时还证明了松贝的质量明显好于后两者。(4)经水和甲醇提取后,原药材提取物中总生物碱和总皂苷等有效成分的相对含量得到了富集。川贝与其他几种贝母的水提物与醇提物的红外光谱中1100cm-1与1630cm-1附近的相对峰强度明显不同,这也与传统观念所认为的川贝的药效优于其他品种贝母的观点相一致。研究中还发现贝母水提物的红外光谱中有1120±5、618cm-1等硫酸盐的特征吸收峰,这与其加工过程中使用硫磺熏蒸等处理有关,说明通过红外光谱还可以对贝母中的硫残留进行检测。
综上所述,红外光谱三级宏观指纹鉴定技术结合计算机比对软件技术在中药质量控制中具有良好的应用前景。
Bulbus Fritillariae (in Chinese named Beimu), referred to the bulbs of several Fritillaria species (Liliaceae), is a commonly used anti-tussive and expectorant herb in traditional Chinese medicine (TCM) for more than 2000 years which is also used as a dietary supplement in China.
Because there are many varieties of herbal medicine, which are the same as Beimu belong to Fritillaria, they are quite similar, and different parts and producing areas of Beimu have diverse chemical constituents and drug effects. Therefore, rapid and accurate identification method can play a significant role on guaranteeing their curative effect. Infrared spectroscopy (IR) is one of the routine means to distinguish chemical compounds and confirm material structures. The IR spectra of Traditional Chinese Medicine (TCM) include spectra of each compound in the system, which shows the whole information of TCM.
In this thesis, we have analyzed and identified the quality of Beimu via the multi-steps IR macro-fingerprint method and combined with the software of Computer Analysis Comparison. The main conclusions include:(1) Feral Bulbus Fritillariae Cirrhosae(CB) and feral Bulbus Fritillariae Ussuriensis(UB) of different origins are quite different, the reason of which is that they have quite different grown conditions of climatic conditions, topography, soil and so on. So, these distinction leads to the content of their chemical components. Beimu in the same province are quite similar but not the same. It is thus clear that the influence of the kind of Beimu chemical components by the different origins is not so big while it is big in the content accumulation. (2) The IR spectra of the different kinds of Beimu materials shows that CB and Bulbus Fritillariae Thunbergii (TB) both have a obvious peak at 1647 cm-1 while the peak of other three Beimu is at 1654 cm-1. In the second derivative IR spectra, CB has the strongest peak at 1647 cm-1, TB changed into two peaks at 1640 cm-1 and 1628 cm-1, while other three Beimu are quite similar at 1638cm-1 and 1627cm-1. The three peaks characteristic intensity in the region at 1200-1300cm-1 of the 2D-IR spectra correspond the stretching of the -C-O-C-groups. (3) The research of three different CB:Songbei(SB), Qingbei(QB), Lubei(LB) shows that the different parts of the bulbs contains different active principle. The bud and scale leaf of SB contain dissimilitude active principle with QB and LB. The bud also contains the same starch and active principle with the bulb. So, this is consistent with the rules of pharmacopeia that not remove the bud of CB when using them. Meanwhile, it is also identified that the quality of SB is much better than the other two. (4) The starch contained in the original medicinal extracts has greatly reduced, while the relative content of the effective components, such as the total alkaloid and saponins, has increased. The IR spectrums of the aqueous and alcohol extract of F. cirrhosae are distinctly different with the relatively peak intensity with the other Beimu at 1100cm-1 and 1630cm-1. And We can find peaks at 1120±5 and 618cm-1 in the IR spectrum of Beimu aqueous extract which are the characteristic absorption peaks of the sulfate, and this is related to the use of sulfur fumigation in the processing. And it is also show that the sulphur residue in Beimu can be identified by the FTIR.
In a word, the multi-steps IR Macro-Fingerprint method and combined with the software of Computer Analysis Comparison have great applying foreground in the quality control of TCM area.
引文
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