药对干姜—高良姜挥发油化学成分及中药丹参指纹图谱研究
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摘要
中药的化学成分种类繁多,含量差异很大,构成了非常复杂的分析体系,如何准确地分析中药成分,评价药品质量,阐明中药药理作用一直是比较困难的问题。近年来随着联用仪器：如高效液相色谱-二级管阵列(HPLC-DAD)、高效液相色谱-质谱(HPLC-MS)、气相色谱-质谱(GC-MS)等现代化检测仪器的出现,加上化学计量学理论方法的支持,如交互移动窗口因子分析法(Alternative Moving Window Factor Analysis, AMWFA)、直观推导式演进特征投影法(Heuristic evolving latent projections, HELP)等方法都广泛应用于分析数据的解析,很好的将色谱分离能力与光谱定性能力有机结合,从而使准确定性定量中药成分,科学评价中药质量,合理解释中药药理作用成为可能。
本文以中药药对干姜-高良姜及广泛应用的中药丹参为研究对象,利用联用色谱仪器结合化学计量学分析的方法,测定了其含有挥发油的种类、含量及讨论了在配伍前后的变化；同时完成了丹参指纹图谱的构建。本文内容大体可以分为以下两部分：
一.利用气相色谱-质谱(GC-MS)联用仪器对单味药干姜、高良姜及其药对的挥发油成分进行检测,进一步利用交互移动窗口因子分析法(Alternative Moving Window Factor Analysis, AMWFA)对它们的共有成分进行分析,利用直观推导式演进特征投影法(Heuristic evolving latent projections, HELP)对色谱图中的重叠峰、包埋峰进行解析。
结果表明：药对干姜-高良姜的挥发油成分是两种单味药成分的加合。其中干姜的挥发油成分鉴定了33种,占挥发油总量的80.03%；高良姜的挥发油成分鉴定了46种,占总量的85.96%；药对的挥发油成分鉴定了48种,占总量的81.09%。同时药对中出现了16种新的化学成分,它们的相对含量为2.55%。
二.利用高效液相色谱-二级管阵列(HPLC-DAD)联用仪器分析了30批次不同产地、不同炮制方法的丹参含有的化学成分,构建了丹参的指纹图谱,并得到了不同批次丹参指纹图谱的共有模式。
结果说明：丹参在炮制的过程中,虽然出现了部分化学成分缺失或转化成新物质,但对四种主要成分的定量分析及指纹图谱的整体相似度来看,丹参药材在加工炮制过程中并未造成大量成分的变化和重要活性成分的缺失,加工得到的3类炮制品化学成分基本一致。由此说明采用该炮制工艺处理丹参是合理可行的,利用HPLC-DAD构建中药指纹图谱是科学评价中药质量的有效方法。
本文为中药配伍规律的研究和中药质量控制方法的发展提供了一定的实验基础。
Traditional Chinese medicine (TCM) is composed with numbers of different compounds, which makes evaluate its quality and analyze its pharmaceutical function more difficult. Modern analytic science focuses on overcoming this problem. With the progress of modern science, more and more advanced analytic instruments have been used widely, such as HPLC-DAD、HPLC-MS、GC-MS and so on. Besides of this, the advance of chemometric techniques have also supported the analytic work in basis of theory, like Heuristic Evolving Latent Projections (HELP) and Alternative Moving Window Factor Analysis (AMWFA) which are widely used in analysis of experimental data. Taking advantage of the excellent separation ability of chromatography with the good qualitative ability of spectrometry, it makes the qualitative and quantitative analysis for TCM, evaluate the quality of TCM and explain the pharmaceutical effect of TCM much easier.
In this paper, we want to research the volatile chemical components of herb pair (HP) Rhizoma Zingibers(RZ)-Rhizoma Alpinia Officinarum(RAO), discuss their difference in different uses, and finish constructing the fingerprint of Salvia miltiorrhiza by hyphenated instruments combined with chemometric resolution methods. Overall, the paper could be divided into two main parts as below.
1. Qualitative and quantitative analysis of the volatile chemical components in herb pairs Rhizoma Zingibers-Rhizoma Alpinia Officinarum(RZ-RAO) and its single herb by hyphenated GC-MS combined with chemometric methods AMWFA and HELP.
The experiment shown that the volatile compounds of herb pairs RZ-RAO are from every single herb.33 chemical compounds of RZ、46 chemical components in singer RAO and 48 chemical components in HP (RZ-RAO) were identified, separately representing 80.03%、85.96% and 81.09% of the total content. Among the essential oils of RZ-RAO,16 new chemical compounds occurred, representing 2.55% of the total content.
2. Analysis of the chemical components in 30 batches Salvia miltiorrhiza collected from different places and processed by different methods with hyphenated HPLC-DAD. Finally, the fingerprint of Salvia miltiorrhiza and their common mode were constructed.
Although some chemical compounds lost and some new ones occurred during the process of modification, the content of main components in Salvia miltiorrhiza were nearly the same and its fingerprint still kept stable. It is concluded from the experiment that this process is sensible. And the fingerprint described by HPLC chromatogram is an excellent way to evaluate TCM.
The result of this paper could provide experimental basis for the further research about TCM.
本文以中药药对干姜-高良姜及广泛应用的中药丹参为研究对象,利用联用色谱仪器结合化学计量学分析的方法,测定了其含有挥发油的种类、含量及讨论了在配伍前后的变化；同时完成了丹参指纹图谱的构建。本文内容大体可以分为以下两部分：
一.利用气相色谱-质谱(GC-MS)联用仪器对单味药干姜、高良姜及其药对的挥发油成分进行检测,进一步利用交互移动窗口因子分析法(Alternative Moving Window Factor Analysis, AMWFA)对它们的共有成分进行分析,利用直观推导式演进特征投影法(Heuristic evolving latent projections, HELP)对色谱图中的重叠峰、包埋峰进行解析。
结果表明：药对干姜-高良姜的挥发油成分是两种单味药成分的加合。其中干姜的挥发油成分鉴定了33种,占挥发油总量的80.03%；高良姜的挥发油成分鉴定了46种,占总量的85.96%；药对的挥发油成分鉴定了48种,占总量的81.09%。同时药对中出现了16种新的化学成分,它们的相对含量为2.55%。
二.利用高效液相色谱-二级管阵列(HPLC-DAD)联用仪器分析了30批次不同产地、不同炮制方法的丹参含有的化学成分,构建了丹参的指纹图谱,并得到了不同批次丹参指纹图谱的共有模式。
结果说明：丹参在炮制的过程中,虽然出现了部分化学成分缺失或转化成新物质,但对四种主要成分的定量分析及指纹图谱的整体相似度来看,丹参药材在加工炮制过程中并未造成大量成分的变化和重要活性成分的缺失,加工得到的3类炮制品化学成分基本一致。由此说明采用该炮制工艺处理丹参是合理可行的,利用HPLC-DAD构建中药指纹图谱是科学评价中药质量的有效方法。
本文为中药配伍规律的研究和中药质量控制方法的发展提供了一定的实验基础。
Traditional Chinese medicine (TCM) is composed with numbers of different compounds, which makes evaluate its quality and analyze its pharmaceutical function more difficult. Modern analytic science focuses on overcoming this problem. With the progress of modern science, more and more advanced analytic instruments have been used widely, such as HPLC-DAD、HPLC-MS、GC-MS and so on. Besides of this, the advance of chemometric techniques have also supported the analytic work in basis of theory, like Heuristic Evolving Latent Projections (HELP) and Alternative Moving Window Factor Analysis (AMWFA) which are widely used in analysis of experimental data. Taking advantage of the excellent separation ability of chromatography with the good qualitative ability of spectrometry, it makes the qualitative and quantitative analysis for TCM, evaluate the quality of TCM and explain the pharmaceutical effect of TCM much easier.
In this paper, we want to research the volatile chemical components of herb pair (HP) Rhizoma Zingibers(RZ)-Rhizoma Alpinia Officinarum(RAO), discuss their difference in different uses, and finish constructing the fingerprint of Salvia miltiorrhiza by hyphenated instruments combined with chemometric resolution methods. Overall, the paper could be divided into two main parts as below.
1. Qualitative and quantitative analysis of the volatile chemical components in herb pairs Rhizoma Zingibers-Rhizoma Alpinia Officinarum(RZ-RAO) and its single herb by hyphenated GC-MS combined with chemometric methods AMWFA and HELP.
The experiment shown that the volatile compounds of herb pairs RZ-RAO are from every single herb.33 chemical compounds of RZ、46 chemical components in singer RAO and 48 chemical components in HP (RZ-RAO) were identified, separately representing 80.03%、85.96% and 81.09% of the total content. Among the essential oils of RZ-RAO,16 new chemical compounds occurred, representing 2.55% of the total content.
2. Analysis of the chemical components in 30 batches Salvia miltiorrhiza collected from different places and processed by different methods with hyphenated HPLC-DAD. Finally, the fingerprint of Salvia miltiorrhiza and their common mode were constructed.
Although some chemical compounds lost and some new ones occurred during the process of modification, the content of main components in Salvia miltiorrhiza were nearly the same and its fingerprint still kept stable. It is concluded from the experiment that this process is sensible. And the fingerprint described by HPLC chromatogram is an excellent way to evaluate TCM.
The result of this paper could provide experimental basis for the further research about TCM.
引文
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