化学计量学应用于中药分析和指纹图谱构建的研究
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摘要
“回归自然”、崇尚天然药物正在成为一种世界性潮流，我国中药现代化事业因此面临新的机遇与挑战。中草药是一类十分复杂的黑色分析体系，中药的药效是通过其所含的几十上百种化学成分相互作用的综合结果。化学问题可说是中药现代化的“瓶颈问题”，化学问题不解决，则药理研究无法深入，生产工艺和产品质量缺乏科学的评价指标。本论文分为两个的部分。第一部分从微观入手，着重分析中药的主要化学成分，第二部分从宏观入手，研制中药指纹图谱，以期首先解决评价指标问题。
辽五味子(Schisandra chinensis(Turcz.)Baill.)是木兰科植物五味子的干燥成熟果实，中医作为收敛、滋补强壮剂已有悠久历史。在第二章中，以二维联用色谱仪器GC-MS和化学计量学发展的多元分辨技术对辽五味子果实的挥发油进行了定性定量分析，给出了辽五味子果实挥发油较全面的化学成分信息，为以后进行深入药理研究打下了基础。
我国还有许多以挥发性成分为有效成分的中药材，探讨不同的提取方法对挥发性成分的提取收率和化学组成成分的影响无疑是比较有意义的。第三章中以提取辽五味子果实挥发性成分为例，比较了六种提取方法中挥发性成分的收率变化和化学组成的变化。这些结论对真正用于生产的中药材的挥发性成分的提取无疑是有帮助的。
出于研究鱼腥草注射液指纹图谱的需要，在第四章中以二维联用色谱仪器GC-MS和多元分辨技术对湖南怀化产鱼腥草鲜草的挥发油进行了定性定量分析，掌握了鱼腥草挥发油较全面的化学成分信息，为建立鱼腥草注射液色谱指纹图谱标准打下了基础。
相对化学物质的紫外可见光谱和红外光谱的连续性，化学物质的质谱是不连续的，且每一个质荷比都有明确的物理意义，并对于定性分析极为重要。所以能够对质谱数据进行平滑或去噪而使信噪比提高的方法对定性分析非常重要。二维联用色谱质谱仪器，如高效液相色谱与质谱联用仪(HPLC-MS)、气相色谱与质谱联用仪(GC-MS)，在中药材这样的复杂分析体系的研究中是有力的工具。在第五章中讨论了利用平滑方法克服GC-MS数据中的不等性噪声，提高信噪比，对含量较低的化学成分得到了更准确的定性定量结果。
为更进一步处理二维气相色谱质谱数据，根据随机噪声和噪声信号的质量色谱峰的不同性质，在第六章中提出了基于局部平滑的化合物确认方法。除去色谱
卜D：论义：化学计挞学应用」－中药分析和指纹图趴构建的叽九2002斗9川
峰中的随机噪声后，可较为准确地得到该色谱峰所对应物质的分于离于或准分于
离于的信息，可显著地提高质谱定性分析的准确度。值得指出的是，第五章和第
六章的方法，虽然以GC－MS数据为例，同样适用于HPLC－MS数据。
第七章闸述了本实验室籍化学计量学的信号处理、图像分析和多元统计等方
沾构业的们It’I朴肺B助中药指纹图谱相似度计算软件》。介绍了该软件的数扼压
缩，数折门叫了和数据个移等功能。从理论上讲，色谱方法和光谱、波谱方法均可
＊于制定中药指纹图谱。根据经验，对于一些成分简单、在薄层色谱Ohn＊叫er
Chrolnatography，TLC）卜分离度较好的供试品，则可采用薄层扫描。薄层扫拙得
到的是彩色或黑白的色谱图像，只有先将其数字化，方可使川《计算机辅助小药
指纹图订ND＿1似度计算软件》来w价，我们编写了简单的薄层色谱图像数字化软件。
最后，简要介绍了我们制订鱼腥草注射液和正清风痛宁注射液的色谱指纹图谱的
进展。隋况。
Traditional Chinese medicine(TCM) has become a thriving industry, not just in China, but worldwide. In many cases, toxicity or side
effects associated with Western Medicine have worsened human diseases, which make people more inclined to try natural medicine, and traditional methods of treatment. In the new century, TCM will meet with great changes in both scientific development and social life. They will create both opportunities and challenges for TCM. Some experts have even forecast that the 21st century will be the era of TCM, with the modernization of TCM, it may become the cornerstone of Chinese industries. TCM is an analytical system with too much complexity. The pharmaceutical activity of TCM come from the interactional of all the chemical components in it. The explicit characterization of chemical substance has become the bottleneck in the process of TCM standardization and internationalization. There is two way to overcome the bottleneck, they would be discussed in details in the thesis. One side,
analyze the detailed chemical components in the TCM, another side, develop the fingerprint of the TCM to meet the authentication and quality control of TCM.
The essential oil of Schisandra chinensis(Turcz.)Baill. was analyzed with GC/MS, heuristic evolving latent projections(HELP) resolution and overall volume integration method. HELP method along with the data from GC/MS can conduct the peak purity examination and resolution of overlapping peaks to obtain pure chromatogram and MS spectrum of each component. 56 components are separated and 49 of them were qualitatively and quantitatively analyzed. All the components represent about 98.27% of the total content. The resolved pure chromatogram and MS spectrum can greatly enhance the reliability of similar searches in the commercial MS database and thus contribute to the accuracy of the qualitative and quantitative analysis of the essential oil.
The two-dimensional data obtained from GC/MS is investigated to determine qualitatively and quantitatively chemical components of volatile factions in
Schisandra chinensis (Turcz.) Baill. from six different extraction methods. Subwindow factor analysis (SFA) was specially used to confirm the same components determined from different samples. With the help of SFA and other chemometric techniques, detection of peak purity in chromatograms can be first addressed, and then overlapping peaks arc resolved into the pure chromatographic profile and mass spectrum of each component. The results obtained show that the accuracy of qualitative and quantitative analysis could be greatly enhanced by the chemometric resolution methods. The chemometric resolution techniques upon the two-dimensional data can be quite promising tools for the analysis of the complex samples like traditional Chinese medicines. It is also found that different extraction methods obtain different chemical components both in quality and quantity aspects for the volatile fraction of Schisandra chinensis (Turcz.)Baill..
The GC/MS data from essential oil of Houttuynia cordata Thunb in Huaihua, Hunan province, were resolved with chemometrics resolution method and local smoothing for component identification method. 55 components were elucidated by qualitative and quantitative analysis. The results will be most important in the
development of the fingerpprint for the Houttuynia injection.
In order to improve detection ability and quality of resolution of overlapping peaks with low signal to noise ratio data obtained from GC-MS, the effect of heteroscedastic noises is investigated in the present paper. A new index named smoothing distortion is first developed for evaluating the smoothing efficiency. Roughness penalty smoothing method recently appearing in chemometrics is then compared with wavelet de-noising technique and convolution smoothing approach under condition of heteroscedastic noises. The performance of the methods is assessed using both simulated and experimental GC-MS data. The results obtained show that the roughness penalty method can not o
辽五味子(Schisandra chinensis(Turcz.)Baill.)是木兰科植物五味子的干燥成熟果实，中医作为收敛、滋补强壮剂已有悠久历史。在第二章中，以二维联用色谱仪器GC-MS和化学计量学发展的多元分辨技术对辽五味子果实的挥发油进行了定性定量分析，给出了辽五味子果实挥发油较全面的化学成分信息，为以后进行深入药理研究打下了基础。
我国还有许多以挥发性成分为有效成分的中药材，探讨不同的提取方法对挥发性成分的提取收率和化学组成成分的影响无疑是比较有意义的。第三章中以提取辽五味子果实挥发性成分为例，比较了六种提取方法中挥发性成分的收率变化和化学组成的变化。这些结论对真正用于生产的中药材的挥发性成分的提取无疑是有帮助的。
出于研究鱼腥草注射液指纹图谱的需要，在第四章中以二维联用色谱仪器GC-MS和多元分辨技术对湖南怀化产鱼腥草鲜草的挥发油进行了定性定量分析，掌握了鱼腥草挥发油较全面的化学成分信息，为建立鱼腥草注射液色谱指纹图谱标准打下了基础。
相对化学物质的紫外可见光谱和红外光谱的连续性，化学物质的质谱是不连续的，且每一个质荷比都有明确的物理意义，并对于定性分析极为重要。所以能够对质谱数据进行平滑或去噪而使信噪比提高的方法对定性分析非常重要。二维联用色谱质谱仪器，如高效液相色谱与质谱联用仪(HPLC-MS)、气相色谱与质谱联用仪(GC-MS)，在中药材这样的复杂分析体系的研究中是有力的工具。在第五章中讨论了利用平滑方法克服GC-MS数据中的不等性噪声，提高信噪比，对含量较低的化学成分得到了更准确的定性定量结果。
为更进一步处理二维气相色谱质谱数据，根据随机噪声和噪声信号的质量色谱峰的不同性质，在第六章中提出了基于局部平滑的化合物确认方法。除去色谱
卜D：论义：化学计挞学应用」－中药分析和指纹图趴构建的叽九2002斗9川
峰中的随机噪声后，可较为准确地得到该色谱峰所对应物质的分于离于或准分于
离于的信息，可显著地提高质谱定性分析的准确度。值得指出的是，第五章和第
六章的方法，虽然以GC－MS数据为例，同样适用于HPLC－MS数据。
第七章闸述了本实验室籍化学计量学的信号处理、图像分析和多元统计等方
沾构业的们It’I朴肺B助中药指纹图谱相似度计算软件》。介绍了该软件的数扼压
缩，数折门叫了和数据个移等功能。从理论上讲，色谱方法和光谱、波谱方法均可
＊于制定中药指纹图谱。根据经验，对于一些成分简单、在薄层色谱Ohn＊叫er
Chrolnatography，TLC）卜分离度较好的供试品，则可采用薄层扫描。薄层扫拙得
到的是彩色或黑白的色谱图像，只有先将其数字化，方可使川《计算机辅助小药
指纹图订ND＿1似度计算软件》来w价，我们编写了简单的薄层色谱图像数字化软件。
最后，简要介绍了我们制订鱼腥草注射液和正清风痛宁注射液的色谱指纹图谱的
进展。隋况。
Traditional Chinese medicine(TCM) has become a thriving industry, not just in China, but worldwide. In many cases, toxicity or side
effects associated with Western Medicine have worsened human diseases, which make people more inclined to try natural medicine, and traditional methods of treatment. In the new century, TCM will meet with great changes in both scientific development and social life. They will create both opportunities and challenges for TCM. Some experts have even forecast that the 21st century will be the era of TCM, with the modernization of TCM, it may become the cornerstone of Chinese industries. TCM is an analytical system with too much complexity. The pharmaceutical activity of TCM come from the interactional of all the chemical components in it. The explicit characterization of chemical substance has become the bottleneck in the process of TCM standardization and internationalization. There is two way to overcome the bottleneck, they would be discussed in details in the thesis. One side,
analyze the detailed chemical components in the TCM, another side, develop the fingerprint of the TCM to meet the authentication and quality control of TCM.
The essential oil of Schisandra chinensis(Turcz.)Baill. was analyzed with GC/MS, heuristic evolving latent projections(HELP) resolution and overall volume integration method. HELP method along with the data from GC/MS can conduct the peak purity examination and resolution of overlapping peaks to obtain pure chromatogram and MS spectrum of each component. 56 components are separated and 49 of them were qualitatively and quantitatively analyzed. All the components represent about 98.27% of the total content. The resolved pure chromatogram and MS spectrum can greatly enhance the reliability of similar searches in the commercial MS database and thus contribute to the accuracy of the qualitative and quantitative analysis of the essential oil.
The two-dimensional data obtained from GC/MS is investigated to determine qualitatively and quantitatively chemical components of volatile factions in
Schisandra chinensis (Turcz.) Baill. from six different extraction methods. Subwindow factor analysis (SFA) was specially used to confirm the same components determined from different samples. With the help of SFA and other chemometric techniques, detection of peak purity in chromatograms can be first addressed, and then overlapping peaks arc resolved into the pure chromatographic profile and mass spectrum of each component. The results obtained show that the accuracy of qualitative and quantitative analysis could be greatly enhanced by the chemometric resolution methods. The chemometric resolution techniques upon the two-dimensional data can be quite promising tools for the analysis of the complex samples like traditional Chinese medicines. It is also found that different extraction methods obtain different chemical components both in quality and quantity aspects for the volatile fraction of Schisandra chinensis (Turcz.)Baill..
The GC/MS data from essential oil of Houttuynia cordata Thunb in Huaihua, Hunan province, were resolved with chemometrics resolution method and local smoothing for component identification method. 55 components were elucidated by qualitative and quantitative analysis. The results will be most important in the
development of the fingerpprint for the Houttuynia injection.
In order to improve detection ability and quality of resolution of overlapping peaks with low signal to noise ratio data obtained from GC-MS, the effect of heteroscedastic noises is investigated in the present paper. A new index named smoothing distortion is first developed for evaluating the smoothing efficiency. Roughness penalty smoothing method recently appearing in chemometrics is then compared with wavelet de-noising technique and convolution smoothing approach under condition of heteroscedastic noises. The performance of the methods is assessed using both simulated and experimental GC-MS data. The results obtained show that the roughness penalty method can not o
引文
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