参归生发酊色谱指纹图谱研究
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摘要
中药复方是中医临床用药的主要形式和手段,方以药成,方中各味药又含有多种化学成分,这些固有的化学成分是复方发挥药效作用的物质基础,但方中任一活性成分又不能全面反映中医用药所体现的整体疗效,这是中药复方与化学合成药品在制定质量标准过程中的根本区别,所以宏观的综合分析成为中药复方发展的必然趋势。在寻求综合评价中药复方质量及其量效关系的过程中,值得注意的趋势是色谱指纹图谱的应用。本文以参归生发酊为研究目标,利用二维联用仪器检测并结合化学计量学多元分辨技术实现对其中药复方产品质量控制的研究。
参归生发酊是由丁香、人参、何首乌、红花、侧柏叶、丹参、冬虫夏草、当归和骨碎补九味药材提取、精制而成。由于此中药复方相当复杂,研究主要涉及了几个方面:对构成其主要挥发性部分的丁香药材,和主要非挥发性部分的人参、何首乌药对分别进行深入探讨,并建立其指纹图谱实现对中药及中药复方质量控制的研究。
第一章、简要介绍了我国中药及中药复方质量控制的现状,中药指纹图谱,现代分析技术在中药指纹图谱中的应用以及化学计量学多元分辨技术在中药控制中的应用等内容。
第二章、对紫丁香果和紫丁香叶挥发油的化学成分进行了定性定量分析。采用水蒸气蒸馏的方法提取挥发油,利用GC-MS和化学计量学以及双柱色谱保留指数的方法对各个色谱峰定性,并用色谱峰面积归一法和HELP法获得各化合物的质量分数。
第三章、利用HPLC-DAD分别定量分析了两种不同提取方法下的人参、何首乌及其药对中皂苷和葸醌等主要活性化学成分,同样基于化学计量学多元分辨技术解析所产生的二维数据,以获得每个样品中每个组分纯色谱流出曲线和光谱图,然后通过对比色谱保留时间和紫外光谱,对人参、何首乌药对及其各单味药非挥发性成分进行对比分析,以了解由单味药配方成复方的过程中其化学成分在质与量上的变化。
第四章、研究参归生发酊的挥发性部分的指纹图谱,利用中药质量评价图谱/数据库实现了23个不同批次产品的标准化、相似度检验、化学模式识别分析,并在同一实验条件下将参归生发酊及其按照处方配成的原药材进行了相关分析,为中药复方参归生发酊的物质组成和质量控制的基础研究提供一种快捷的比较方法。
第五章、研究参归生发酊的非挥发性部分的指纹图谱,以实际角度出发,利用大孔吸附树脂,就超声时间、洗脱剂溶度的选择,检测波长的选择等方面进行了研究,确定了最终的提取检测方法,最终建立了HPLC-DAD指纹图谱,也为参归生发酊的质量控制提供了科学依据。
第六章、建立了参归生发酊指纹图谱相似度评价系统,为厂家跟踪产品质量,改善工艺以提高自身产品质量提供了可靠的手段,为实现我们的最终目标-建立一个参归生发酊的质量控制标准奠定了坚实的基础。
Chinese Traditional Medicine Compound(CTMC)is the major form and method of clinical practice in China.However,there is only very limited knowledge known about their chemical compositions, pharmacokinetics,and metabolomics.This is mainly due to the fact that the CTMC are multi-component systems with components mostly unknown.The current quality standard of CTMC is by measuring the concentration of one or very few markers or active components.Hence, this exists quality control standard could not reflect the real and comprehensive active constituents of CTMC,and therefore inadequate to control the quality of CTMC.During the process of seeking the comprehensive appraisal of the quality of TCMC and,the fingerprint technique would be the practical and feasible mean.In this study,quality control of ShenGui hair-growth tincture can be investigated with two-dimensional hyphenated chromatographic instruments and some chemometric multi-resolution method.
ShenGui hair-growth tincture is a kind of herbal preparation for hair loss treatment,which is form of extraction and refinement of Oriental arborvitae,Aweto,Angelica,Radix Salivae Miltiorrhizae,Clove, Safflower,Polygonum multiflorum Thunb,Panax,Drynaria Rhizoma。Because of the complexity of CTMC system,the primary purpose of this work is to use hyphenated instruments and chemometric approaches to analyze TCMC(single medicine and compound medicine).In all,this thesis covers six aspects as below:
1.In the introduction part of this thesis,the recent development of quality control,chromatographic fingerprints,modern analytical techniques and chemometric methods with their application to TCM and CTMC are summarized.
2.Qualitative and quantitative analysis of components in the compositions in the essential oils from fruits and leaves of Lilac. Essential oils were extracted by water distillation and analyzed by capillary gas chromatography-mass spectrometry as well as chemometrics resolution method and retention indices(I~T)on two columns with different polarity.The relative contents of the identified components in the essential oils were obtained by normalization of peak areas and HELP.
3.Quantitative analysis of of two kinds of bioactive constituents in Traditional Chinese Medicine-herb pair(TCM-HP)of Ginseng and Ploygonum multiforum(PM),saponins and anthraquinone derivatives, was studied in different extraction methods by high performance liquid chromatography-photodiode array detection(HPLC-DAD)method.With the help of some similar chemometric multi-resolution approaches such as AMWFA upon the two-dimensional data produced,pure chromatogram and UV spectra of each component can be obtained.With the combined information on retention times and UV spectra,chemical components in TCM-HP of Ginseng and PM and its single hebals are qualitatively and quantitatively compared.
4.Chapter four focus on the study of the GC-MS chromtographic fingerprints of ShenGui hair-growth tincture.The standardization of originaldata,examination of similarity degree and analysis of chemical pattern were achieved in Extendable Data-base for Quality Assessment of Traditional Chinese Herbal Medicine.Gas chromatographic-mass spectrometry(GC-MS)profiles of ShenGui hair-growth tincture and those of the corresponding nine raw materials mixture were established were established as their characteristic fingerprints and employed to assess their consistency and difference,which indicated the changes of major constituents in the course of preparation procedure.So it can provide a rapid method for the reach for he complex medicines' quality control.
5.Chapter five focus on the study of the GC-MS chromtographic fingerprints of ShenGui hair-growth tincture.Preparation of samples by adsorption Purification of macroporous resin has been adopted.Final determining methods are obtained after the research on extraction time, the concentration of eluant and HPLC conditions.It is also surely aid to construct the chromatographic fingerprints for quality control of ShenGui hair-growth tincture.
6.A database of ShenGui hair-growth tincture was developed in the sixth part.The performance of this work not only provides reliable means to do quality control,tracking the quality of products and optimizing the course of production,but also provides a good foundation for our finally objective,building a quality control standard of ShenGui hair-growth tincture.
参归生发酊是由丁香、人参、何首乌、红花、侧柏叶、丹参、冬虫夏草、当归和骨碎补九味药材提取、精制而成。由于此中药复方相当复杂,研究主要涉及了几个方面:对构成其主要挥发性部分的丁香药材,和主要非挥发性部分的人参、何首乌药对分别进行深入探讨,并建立其指纹图谱实现对中药及中药复方质量控制的研究。
第一章、简要介绍了我国中药及中药复方质量控制的现状,中药指纹图谱,现代分析技术在中药指纹图谱中的应用以及化学计量学多元分辨技术在中药控制中的应用等内容。
第二章、对紫丁香果和紫丁香叶挥发油的化学成分进行了定性定量分析。采用水蒸气蒸馏的方法提取挥发油,利用GC-MS和化学计量学以及双柱色谱保留指数的方法对各个色谱峰定性,并用色谱峰面积归一法和HELP法获得各化合物的质量分数。
第三章、利用HPLC-DAD分别定量分析了两种不同提取方法下的人参、何首乌及其药对中皂苷和葸醌等主要活性化学成分,同样基于化学计量学多元分辨技术解析所产生的二维数据,以获得每个样品中每个组分纯色谱流出曲线和光谱图,然后通过对比色谱保留时间和紫外光谱,对人参、何首乌药对及其各单味药非挥发性成分进行对比分析,以了解由单味药配方成复方的过程中其化学成分在质与量上的变化。
第四章、研究参归生发酊的挥发性部分的指纹图谱,利用中药质量评价图谱/数据库实现了23个不同批次产品的标准化、相似度检验、化学模式识别分析,并在同一实验条件下将参归生发酊及其按照处方配成的原药材进行了相关分析,为中药复方参归生发酊的物质组成和质量控制的基础研究提供一种快捷的比较方法。
第五章、研究参归生发酊的非挥发性部分的指纹图谱,以实际角度出发,利用大孔吸附树脂,就超声时间、洗脱剂溶度的选择,检测波长的选择等方面进行了研究,确定了最终的提取检测方法,最终建立了HPLC-DAD指纹图谱,也为参归生发酊的质量控制提供了科学依据。
第六章、建立了参归生发酊指纹图谱相似度评价系统,为厂家跟踪产品质量,改善工艺以提高自身产品质量提供了可靠的手段,为实现我们的最终目标-建立一个参归生发酊的质量控制标准奠定了坚实的基础。
Chinese Traditional Medicine Compound(CTMC)is the major form and method of clinical practice in China.However,there is only very limited knowledge known about their chemical compositions, pharmacokinetics,and metabolomics.This is mainly due to the fact that the CTMC are multi-component systems with components mostly unknown.The current quality standard of CTMC is by measuring the concentration of one or very few markers or active components.Hence, this exists quality control standard could not reflect the real and comprehensive active constituents of CTMC,and therefore inadequate to control the quality of CTMC.During the process of seeking the comprehensive appraisal of the quality of TCMC and,the fingerprint technique would be the practical and feasible mean.In this study,quality control of ShenGui hair-growth tincture can be investigated with two-dimensional hyphenated chromatographic instruments and some chemometric multi-resolution method.
ShenGui hair-growth tincture is a kind of herbal preparation for hair loss treatment,which is form of extraction and refinement of Oriental arborvitae,Aweto,Angelica,Radix Salivae Miltiorrhizae,Clove, Safflower,Polygonum multiflorum Thunb,Panax,Drynaria Rhizoma。Because of the complexity of CTMC system,the primary purpose of this work is to use hyphenated instruments and chemometric approaches to analyze TCMC(single medicine and compound medicine).In all,this thesis covers six aspects as below:
1.In the introduction part of this thesis,the recent development of quality control,chromatographic fingerprints,modern analytical techniques and chemometric methods with their application to TCM and CTMC are summarized.
2.Qualitative and quantitative analysis of components in the compositions in the essential oils from fruits and leaves of Lilac. Essential oils were extracted by water distillation and analyzed by capillary gas chromatography-mass spectrometry as well as chemometrics resolution method and retention indices(I~T)on two columns with different polarity.The relative contents of the identified components in the essential oils were obtained by normalization of peak areas and HELP.
3.Quantitative analysis of of two kinds of bioactive constituents in Traditional Chinese Medicine-herb pair(TCM-HP)of Ginseng and Ploygonum multiforum(PM),saponins and anthraquinone derivatives, was studied in different extraction methods by high performance liquid chromatography-photodiode array detection(HPLC-DAD)method.With the help of some similar chemometric multi-resolution approaches such as AMWFA upon the two-dimensional data produced,pure chromatogram and UV spectra of each component can be obtained.With the combined information on retention times and UV spectra,chemical components in TCM-HP of Ginseng and PM and its single hebals are qualitatively and quantitatively compared.
4.Chapter four focus on the study of the GC-MS chromtographic fingerprints of ShenGui hair-growth tincture.The standardization of originaldata,examination of similarity degree and analysis of chemical pattern were achieved in Extendable Data-base for Quality Assessment of Traditional Chinese Herbal Medicine.Gas chromatographic-mass spectrometry(GC-MS)profiles of ShenGui hair-growth tincture and those of the corresponding nine raw materials mixture were established were established as their characteristic fingerprints and employed to assess their consistency and difference,which indicated the changes of major constituents in the course of preparation procedure.So it can provide a rapid method for the reach for he complex medicines' quality control.
5.Chapter five focus on the study of the GC-MS chromtographic fingerprints of ShenGui hair-growth tincture.Preparation of samples by adsorption Purification of macroporous resin has been adopted.Final determining methods are obtained after the research on extraction time, the concentration of eluant and HPLC conditions.It is also surely aid to construct the chromatographic fingerprints for quality control of ShenGui hair-growth tincture.
6.A database of ShenGui hair-growth tincture was developed in the sixth part.The performance of this work not only provides reliable means to do quality control,tracking the quality of products and optimizing the course of production,but also provides a good foundation for our finally objective,building a quality control standard of ShenGui hair-growth tincture.
引文
[1]姚新生、胡柯.中药复方的现代化研究.化学进展,1999,19(2):192-196
[2]王夔.化学家怎样看中药复方研究.化学进展,1999,19(2):184-185
[3]陈耀祖.中药复方化学研究策略诹议.化学进展,1999,19(2):188-91
[4]谢培山.中药质量控制模式的发展趋势.中药新药与临床药理,2001,12(3):188-191
[5]谢培山.中药色谱指纹图谱鉴别的概念、属性、技术与应用.中国中药杂志,2001,26(10):653-655
[6]谢培山.色谱指纹图谱分析是中草药质量控制的可行策略.中药新药与临床药理,2001,12(3):141-151,169
[7]谢培山.中药制剂色谱指纹图谱(图像)鉴别.中成药,2000,22(6):391-394
[8]李建银,刘文,等.中药复方指纹图谱的研究现状及其前景.武警医学.2004,15(1):59-61
[9]谢培山.中药色谱指纹图谱研究.北京:人民卫生出版社,2005.
[10]Liu C L,Zhu P L,Liu M C.Computer-aided development of a high-performance liquid chromatographic method for the determination of hydroxyanthraquinone derivatives in Chinese herb medicine rhubarb.J.Chromatogr.A,1999,857(1-2):167-174.
[11]Lin G,Li P,Li S L,Chan S W.Chromatographic analysis of Fritillaria isosteroidal alkaloids,the active ingredients of Beimu,the antitussive traditional Chinese medicinal herb.J.Chromatogr.A,2001,935(1-2):321-338.
[12]Tsai T R,Tseng T Y,Chen C F,Tsal T H.J.Identification and determination of geniposide contained in Gardenia jasminoides and in two preparations of mixed traditional Chinese medicines.Chromatogr.A,2002,961(1):83-88.
[13]Kitagawa I.A natural sweetener and an important ingredient in Chinese medicine.Pure Appl.Chem,2002,74(7):1189-1198.
[14]Sanyal U,Bhattacharyya S,Patra A,Hazra B.Liquid chromatographic separation of derivatives of diospyrin,a bioactive bisnaphthoquinonoid plant-product,and analogous naphthyl compounds.J.Chromatogr.A,2003,1017(1-2):225-232.
[15]Thanawiroon C,Linhardt R J.Separation of a complex mixture of heparin-derived oligosaccharides using reversed-phase high-performance liquid chromatography.J.Chromatogr.A,2003,1014(1-2):215-223.
[16]Loganathan D,Wang H M,Mallis L M,Linhardt R J.Structural Variation of the Antithrombin Ⅲ Binding Site and its Occurrence in Heparin from Different Sources.Biochemistry,1990,29:4362-4368.
[17]Desai U R,Wang H M,Kelly T R,Linhardt R J.Structure elucidation of a novel acidic tetrasaccharide and hexasaceharide derived from a chemically modified heparin.Carbohydr.Res.,1993,241:249-259.
[18]Imanari T,Toida T,Koshiishi I,Toyoda H,J.High-performance liquid chromatographic analysis of g;ycosaminoglycan-derived oligosaccharides.Chromatogr.A,1996,720(1-2):275-293.
[19]Leonard S,Capote R,Germonprez N,L.Puyvelde Van,Kimpe N De,Vermeersch H,Rosier J,Maes L,Roets E,Hoogrnartens J.Liquid chromatographic method for analysis of saponins in Maesa balansae extract active against leishmaniasis.J.Chromatogr.A,2003,1012(1)39-46.
[20]Lin CH,Chen B H.Determination of carotenoids in tomato juice by liquid chromatography.J.Chromatogr.A,2003,1012(1):103-109.
[21]Cawthray G R,An improved reversed-phase liquid chromatographic method for the analysis of low-molecular mass organic acids in plant root exudates.J.Chromatogr.A,2003,1011(1-2):233-240.
[22]Lee A W M,Chan W F,Yuen F S Y,Tse K P K,Liang Y Z,Fang K T.An example of a sequential uniform design:Application in capillary electrophoresis.Chemom.Intell.Lab.Syst.1997,39(1):11-18.
[23]刘春丽,刘满仓,朱彭龄.高效液相色谱法分析中药及植物药的进展.分析化学,2000,28(5):631-643
[24]Hayen H,Karst U,Strategies for the liquid chromatographic-mass spectrometric analysis of non-polar compounds.J.Chromatogr.A,2003,1000(1-2):549-565.
[25]Guetens G,De Boeck G,Wood M,Maes R A A,Eggermont A A M,Highley M S,van Oosterom A T,et.al.Hyphenated techniques in anticancer drug monitoring:I.Capillary gas chromatography-mass spectrometry.J.Chromatogr.A,2002,976(1-2):229-238.
[26]龚范,宋又群,彭源贵,梁逸曾,Leung A K M,Chau F T.平胃散中苍术挥发油的GC/MS分析,药学学报,2000,35(5):394-397.
[27]龚范,梁逸曾,宋又群,彭源贵,崔卉,Leung A K M,Chau F T.陈皮挥发油的气相色谱/质谱分析,分析化学2000,28(7):860-864.
[28]Gong F,Liang Y Z,Cui H,Chau F T,Chan B T P.Gas chromatography-mass spectrometry and chemometric resolution applied to the determination of essential oils in Cortex Cinnamomi.J.Chromatogr.A,2001,905(1-2):193-205.
[29]Gong F,Liang Y Z,Xu Q S,Chau F T.Determination of volatile components in peptic powder by gas chromatography-mass spectrometry and chemometric resolution.J.Chromatogr.A,2001,909(2)237-247.
[30]李晓宁,崔卉,宋又群,梁逸曾.辽五味子果实挥发油成分的鉴定.药学学报,2001,36(3):215-219.
[31]龚范,梁逸曾,宋又群,彭源贵,Leung A K M,Chau F T.平胃散挥发性成分的研究(Ⅱ)-厚朴挥发油的GC/MS分析.高等学校化学学报,2001,22(9):1481-1485.
[32]Li X N,LiangY Z.Analysis of the Volatile Fractions of Schisandra Chinensis (Turcz.)Baill.with GC/MS and Chemometric Resolution,Phytochemical Analysis,2003,14:23-33.
[33]Gong F,Liang Y Z.Combination of GC-MS with local resolution for determining volatile components from si-wu decoction,J.Seperation Science,2003,26:112-122.
[34]Li B Y,Hu Y,Liang Y Z,Huang L F,Xu C J,Xie P S.Spectral Correlative Chromatography and Its Application to Analysis of Chromatographic Fingerprints of Herbal Medicines.Journal of Separation Science,2004,27:581-588.
[35]Wang X S,Kapoor V,Smythe G A.Assessment of hydroxyl radical generation and radical scavenging activity of Chinese medicinal herbs using GC-MS.Am.J.Chin.Med,2003,31:927-944.
[36]Fu P P,Yang Y C,Xia Q S,Chou M W,Cui Y Y,Lin G.J.Mutagenic effects of aqueous extracts of Symphytum officinale L.and of its alkaloidal fractions.Food Drug Anal,2002,10(4):198-211.
[37]Tseng M C,Tsai M J,Lin J H,Wen K C H.GC/MS Analysis on Anorectics Adulterated in Traditional Chinese Medicines.J.Food Drug Anal.,2000,8(4):315-330.
[38]Vieira R F,Simon J E,Chemical characterization of Basil(Ocimum spp.)found in the markets and used in traditional medicine in Brazil.Econ.Bot.2002,54:207-216.
[39]Gherman C,Culea M,Cozar O.Comparative analysis of some active principles of herb plants by GC/MS.Talanta,2000,53:253-262.
[40]Velasco-Negueruela A,Perez-Alonso M J,Perez de Paz P L,J Pala-Paul,Sanz J.Analysis by gas chromatography-mass spectrometry of the essential oils from the aerial parts of Rutheopsis herbanica(Bolle)Hans.& Kunk.,gathered in Fuerteventura(Canary Islands).J.Chromatogr.A,2003,984(1):159-162.
[41]Velasco-Negueruela A,Perez-Alonso M J,Perez de Paz P L,Pala-Paul J,Sanz J.Analysis by gas chromatography-mass spectrometry of the essential oil from the aerial parts of Pimpinella junoniae Ceb.& Ort.,gathered in La Gomera,Canary Islands,Spain.J.Chromatogr.A,2003,1011(1-2):241-244.
[42]梁逸曾.白、灰、黑复杂多组分体系及其化学计量学算法.长沙:湖南科学技术出版社,1996
[43]俞汝勤.化学计量学导论.长沙:湖南教育出版社,1991.
[44]高鸿.分析化学现状与未来(“分析化学前沿”主题报告).北京:科学出版社,1991.
[45]国家自然科学基金会.自然科学学科发展战略调研报告.分析化学.北京:科学版社,1993.
[46]Malinowski E R.Factor analysis in chemistry(2~(nd)edition).Wiley,New York,1991.
[47]许禄.化学计量学方法.北京:科学出版社,1994.
[45]Maeder M.Evolving factor analysis for the resolution of overlapping chromatographic peaks.Anal.Chem.,1957,59:527-530
[49]Maeder M.,Zilian A.Evolving factor analysis,a new multivariate techniques in chromatography.Chemom.Intell.Lab.Syst.,1988,3:205-213
[50]Maeder M.,Zuberbuhler A D.The resolution of overlapping chromatographic peaks by evolving factor analysis.Anal.Chim.Acta,1956,181:287-291
[51]Kvalheim O.M.,Liang Y.Z.Heuristic evolving latent projections:resolving two-way multicomponent data.Part 1.Selectivity,latent projective graph,datascope,local rank and unique resolution.Anal.Chem.,1992,64:936-946
[52]Liang Y.Z.,Kvalheim O M,Keller H R,Massart D L,et al.Heuristic evolving latent projections:resolving two-way multicomponent data.Part 2:Detection and resolution of minor constituents.Anal.Chem.,1992,64:946-953
[53]Malinowski E.R.Window factor analysis,theoretic derivation and application to flow injection analysis data.J.Chemom.,1992,6,29-40
[54]Manne R.,Shen H.L.,Liang Y.Z.Subwindow factor analysis.Chemom.Intell.Lab.Syst.,1999,45:171-176
[55]Shen H L,Manne R.,Xu Q.S.,et al.Local resolution of hyphenated chromatographic data.Chemom.Intell.Lab.Syst.,1999,45:323-330
[56]沈海林,梁逸曾,俞汝勤,等.香港大气颗粒物中多环芳烃的HELP法解析.中国科学(B辑),1998,27:556-563
[57]Keller H.R.,Massart D.L..Peak purity control in liquid chromatography with photodiode-array detection by a fixed size moving window evolving factor analysis.Anal.Chim.Acta,1991,246:379-390
[58]Gong F.,Liang Y.Z.,Xu Q.S.,et al.Gas chromatography-mass spectrometry and chemometric resolution applied to the determination of essential oils in Cortex Cinnamomi.J.Chromatogr.A,2001,905:193-205
[59]Gong F.,Liang Y.Z.,Xu Q.S.,et al.Determination of volatile components in peptic powder by Gas chromatography-mass spectrometry and chemometric resolution.J.Chromato.A,2001,909:237-247
[60]Li X.N.,Cui H.,Song Y Q,et al.Analysis of the Volatile Fraction of Schisandra Chinensis(Turcz.)Baill.with GC/MS and Chemometric Resolution.Phytochemical Analysis.Phytochemical Analysis,2003,14:23-33
[61]龚范,梁逸曾,宋又群,等.平胃散挥发性成分的研究(Ⅱ)-厚朴挥发油的GC/MS分析.高等学校化学学报,2001,22(9):1481-1485
[62]亓云鹏,孙胜利,吴玉田,等.直观推导式演进特征投影法测定不同方法提取的国产血竭中龙血素B的含量.分析化学,2002,30(7):797-800
[63]江苏新医学院.中药大辞典,上海:上海大众出版社,2003.
[64]王丹丹,刘盛泉,陈英杰,等.紫丁香有效成分的研究.药学学报,1982,17(12):951-954
[65]薛俊玲,腾慧梅.甲丁胶囊的抗病毒实验研究.中医药信息,1997,2:47
[66]Yan X.J.,Zhou J.J.,Xie G.R.,et al."Traditional Chinese Medicines:Molecular Structures,Natural Sources and Applications",Aldershot,Ashgate,1999
[67]Wagner C.,Sefkow M.,Kopka.Construction and application of a mass spectral and retention time index database generated from plant GC/EI-TOF-MS metabolite profiles.Phytochemistry,2003,62:887-900
[68].Kovats E.Sz.,Gas-chromatographische Charakterisierung organischer Verbindungen.Teil 1:Retentions indices aliphatischer Halogenide,Alkohole, Aldehyde und Ketone.Helv.Chim.Acta,1958,41:1915-1929
[69]Wang Y.H.,Wong EK.Mathematical relationships between vapor pressure,water solubility,Henry's law constant,n-octanol/water partition coefficent and gas chromatographic retention index of polychlorinated-dibenzo-dioxins.Water Research,2002,36:350-355
[70]H.van Den Dool and E Dec.Kratz.A generalization of the retention index system including linear temperature programmed gas—liquid partition chromatography.J.Chromatogr.,1963,11:463-471
[71]Manne R.,Shen H.L.,Liang Y.Z.Subwindow factor analysis.Chemom.Intell.Lab.Syst.,1999,45:171-176
[72]Li B.Y.,Hu Y.,Liang Y.Z.,et al.Spectral Correlative Chromatography and Its Application to Analysis of Chromatographic Fingerprints of Herbal Medicines.J.Separation Science,2004,27:581-588
[73]刘正信,高海翔,郑培清,等.粉绿铁线莲挥发油成分分析.天然产物研究与开发,2001,13(5)25-27
[74]Kvalheim O.M.,Liang Y.Z.Heuristic evolving latent projections:resolving two-way multicomponent data.Part 1.Selectivity,latent projective graph,dataseope,local rank and unique resolution.Anal.Chem.,1992,64:936-946
[75]赵晨曦,梁逸曾.公丁香与母丁香挥发油化学成分的Gc/MS研究,中药现代实践.2004,18:92-95
[81]金国琴,赵伟康.首乌制剂对老年大鼠胸腺、肝脏蛋白质和核酸含量的影响,中草药.1994,25(11):590-591.
[82]应久皓,周学优,朱秀琴.何首乌炮制品药理临床研究.中国中药杂志.1992,17(12):722-724.
[83]魏锡云,张锦堃,罗映辉,等.黄芪和何首乌抗环磷酰胺诱导胸腺细胞凋亡.中国药科大学学报.2000,31(1):35-38.
[84]黄运忠,张树秋,李民,等.乌提取液对小白鼠HDL中胆固醇含量的影响.右江民族医学院学报.1990,12(4):8-10.
[85]段江燕,张金红,许乃寒,等.首乌复方对兔红细胞膜Ca~(2+),Mg~(2+)-ATPase 活性的影响.中草药.2000,31(8):613-614.
[86]徐萃华,李燕娜.何首乌对体外培养肝细胞(7-~3H)-胆固醇掺入的影响.中医药学报.1987,(3):39-40.
[87]吴兆洪,杨永华,刘玉瑾,等.首乌冲剂改善高脂血症与高凝状态的临床观察.中成药.2000,2(12):844-846.
[88]叶定江,朱荃,祁辉林,等.何首乌及其炮制品的免疫药理学研究.中药通报.1987,12(3):21-24.
[89]姚鸣春,罗碧如,蓝开蔚,等.中药何首乌抗衰老作用的研究.药学通报.1984,19(11):28-30.
[90]杨秀伟.何首乌醇提物对易老化小鼠肝脏和脑单胺氧化酶活性的影响.中国中药杂志.1996,21(1):48-49.
[91]胥庆华,刘丽云,赵瑞华,等著.中药药对大全.北京:中国中医药出版社,2004.67-68
[92]鲁佳慧,江滨,曾元儿,等.中药配伍的研究进展.时珍国医国药,2003,14(7):419-421
[93]李晓如,梁逸曾等,中药药对的化学成分研究川芎.赤芍挥发油的GC-MS 分析.高等学校化学学报,2006,(2007);443-448
[94]何佳霞,蒋盂良,冯映冰,等.芍药汤配伍的化学变化研究.中国中药杂志,1998,23(7):432-434
[95]徐艳春,魏璐雪,周玉新,等.高效液相法测定黄连与吴茱萸配伍前后吴茱萸碱及吴茱萸次碱的含量.中国中药杂志,2001,26(12):846-849
[96]黄熙,任平,王骊丽,等.不同煎煮方法和配伍因素对汤剂中阿魏酸含量的影响.中草药,2001,32(5):41-45
[97]涂瑶生,刘法锦,孙冬梅,等.清胃散单煎与合煎中盐酸小檗碱含量的测定.中国中医基础医学杂志,2000,6(8):531-533
[98]袁久荣.四物汤的实验研究.中国中药杂志,1999,16(3):153-155
[99]曾慧芳,苏子仁,史俏蓉,等.虎杖单煎、复方共煎过程中的物理化学变化初探.中国药房,1999,10(3):112-113
[100]容蓉,袁久荣.四物汤及其配伍组方中苯甲酸煎出量的HPLC法测定.中草药,2001,32(2):114-115
[101]张宇,陈丽艳,杨义,等.四逆汤口服液中附子与甘草配伍前后有效成分变化.佳木斯医学院学报,1996,19(1):27-30
[102]崔健,耿惠,刘淑杰,等.山豆根在复方中化学成分变化的研究.中草药,2001,32(7):613-614
[103]夏云,李志明,朱丹妮,等.生脉散复方化学动态变化与药效关系的研究.中国中药杂志,1998,23(4):230-231
[104]涂瑶生,刘法锦,孙冬梅,等.单味中药浓缩颗粒组成的三利降脂方与煎提取物的化学成分比较.中药新药与临床药理,1998,9(2):108-120
[105]张志伟.汤剂合煎与分煎混合所得成分之初探.中成药研究,1986,7(4): 41-42
[106]谭洪根,刘应泉,冯维秀,等.芍药甘草汤配伍的化学成分研究.中国中药杂志,1995,20(9):550-551
[107]陈建萍,吴伟康,张敏生,等.中药复方配伍规律研究的思路与方法.中国实验方剂学杂志,2000,6(1):1-4
[108]王庆国,韩学杰,李成为.冠心病临床药对新用.中国医药科技出版社.2005
[109]Kvalheim O M,Liang Y Z.Heuristic evolving latent projections-resolving 2-way multicomponent data.1.Selectivity,latent-projective graph,datascope,local rank and unique resoltuion.Anal.Chem.1992,64(8):936-946.
[110]Liang Y Z,Kvalheim O M,Keller H R,et.al.Heuristic evolving latent projections- Resolving 2-way multicomponent data.2.Detection and resolution of minor constituents.Anal.Chem.,1992,64(8):946-953.
[111]Cheng Y Y,Chen M J,Tong W D.An Approach of comparative analysis of Chromatographic Fingerprints for Assuring the Quality of Botanical Drugs.J.Chem.Inf.Comput.Sci.,2003,43:1068-1076
[112]梁逸曾,谢培山.指纹图谱的化学模式识别分析-若干实质性问题的探讨.世界科学技术-中药现代化,2002,4(5):47-51
[113]Cheng Y Y,Chen M J,Tong W D.An Approach of comparative analysis of Chromatographic Fingerprints for Assuring the Quality of Botanical Drugs.J.Chem.Inf.Comput.Sci.,2003,43:1068-1076
[114]Woo Y H,Kim H J,Cho J H.Identifivation of herbal medicines using recognition techniquesWith near-infrared reflectance.Microchemical Joural,1999,63:61-70
[115]陈念贻,钦佩,陈瑞亮等.模式识别方法在化学化工中的应用.北京:科学出版社,2000
[116]Welsh W J,Lin W,Terignl S H,et al.Pharmaceutical fingerprinting:Evaluation of neural networks and chemometric techniques for distinguishing among same-product manufractures.Anal.Chem.1996,68:3473-3482
[117]屈凌波,相柄仁,安登奎.人工神经网络在中药模式识别中的应用.计算机与应用化学,200,19(4):428-431
[118]罗旭,毕开顺,王玺等.中药质量化学模式识别研究进展.药学学报,1993,28(12):936-940
[119]Wold H.Estimation of principal components and related models by iterative least squares.In:Krishnaiah P R,eds.Multiuariate analysis.New York: Academic Press, 1966. 391-420.
[120] Jong de S. SIMPLS: an alternative approach squares regression. Chemometrics and Intelligent Laboratory Systems, 1993,18 (3): 251-263.
[121] Brown C W, Lynch P F, Obremski R J, et al. Matrix representations and criteria for selecting analytical wavelengths for multicomponent spectroscopic analysis. Analytical Chemistry, 1982,54(9): 1472-1479.
[122] Kisner H J, Brown C W, Kavarnos G J. Multiple analytical frequencies and standards for the least-squares spectrometric analysis of serum lipids. Analytical Chemistry, 1983,55(11): 1703-1707.
[123] Golub G, Kalian W. Calculating the singular values and pseudo-inverse of a matrix. Journal of the Society for Industrial and Applied Mathematics: Series B, Numerical Analysis, 1965,2(2):205-224.
[2]王夔.化学家怎样看中药复方研究.化学进展,1999,19(2):184-185
[3]陈耀祖.中药复方化学研究策略诹议.化学进展,1999,19(2):188-91
[4]谢培山.中药质量控制模式的发展趋势.中药新药与临床药理,2001,12(3):188-191
[5]谢培山.中药色谱指纹图谱鉴别的概念、属性、技术与应用.中国中药杂志,2001,26(10):653-655
[6]谢培山.色谱指纹图谱分析是中草药质量控制的可行策略.中药新药与临床药理,2001,12(3):141-151,169
[7]谢培山.中药制剂色谱指纹图谱(图像)鉴别.中成药,2000,22(6):391-394
[8]李建银,刘文,等.中药复方指纹图谱的研究现状及其前景.武警医学.2004,15(1):59-61
[9]谢培山.中药色谱指纹图谱研究.北京:人民卫生出版社,2005.
[10]Liu C L,Zhu P L,Liu M C.Computer-aided development of a high-performance liquid chromatographic method for the determination of hydroxyanthraquinone derivatives in Chinese herb medicine rhubarb.J.Chromatogr.A,1999,857(1-2):167-174.
[11]Lin G,Li P,Li S L,Chan S W.Chromatographic analysis of Fritillaria isosteroidal alkaloids,the active ingredients of Beimu,the antitussive traditional Chinese medicinal herb.J.Chromatogr.A,2001,935(1-2):321-338.
[12]Tsai T R,Tseng T Y,Chen C F,Tsal T H.J.Identification and determination of geniposide contained in Gardenia jasminoides and in two preparations of mixed traditional Chinese medicines.Chromatogr.A,2002,961(1):83-88.
[13]Kitagawa I.A natural sweetener and an important ingredient in Chinese medicine.Pure Appl.Chem,2002,74(7):1189-1198.
[14]Sanyal U,Bhattacharyya S,Patra A,Hazra B.Liquid chromatographic separation of derivatives of diospyrin,a bioactive bisnaphthoquinonoid plant-product,and analogous naphthyl compounds.J.Chromatogr.A,2003,1017(1-2):225-232.
[15]Thanawiroon C,Linhardt R J.Separation of a complex mixture of heparin-derived oligosaccharides using reversed-phase high-performance liquid chromatography.J.Chromatogr.A,2003,1014(1-2):215-223.
[16]Loganathan D,Wang H M,Mallis L M,Linhardt R J.Structural Variation of the Antithrombin Ⅲ Binding Site and its Occurrence in Heparin from Different Sources.Biochemistry,1990,29:4362-4368.
[17]Desai U R,Wang H M,Kelly T R,Linhardt R J.Structure elucidation of a novel acidic tetrasaccharide and hexasaceharide derived from a chemically modified heparin.Carbohydr.Res.,1993,241:249-259.
[18]Imanari T,Toida T,Koshiishi I,Toyoda H,J.High-performance liquid chromatographic analysis of g;ycosaminoglycan-derived oligosaccharides.Chromatogr.A,1996,720(1-2):275-293.
[19]Leonard S,Capote R,Germonprez N,L.Puyvelde Van,Kimpe N De,Vermeersch H,Rosier J,Maes L,Roets E,Hoogrnartens J.Liquid chromatographic method for analysis of saponins in Maesa balansae extract active against leishmaniasis.J.Chromatogr.A,2003,1012(1)39-46.
[20]Lin CH,Chen B H.Determination of carotenoids in tomato juice by liquid chromatography.J.Chromatogr.A,2003,1012(1):103-109.
[21]Cawthray G R,An improved reversed-phase liquid chromatographic method for the analysis of low-molecular mass organic acids in plant root exudates.J.Chromatogr.A,2003,1011(1-2):233-240.
[22]Lee A W M,Chan W F,Yuen F S Y,Tse K P K,Liang Y Z,Fang K T.An example of a sequential uniform design:Application in capillary electrophoresis.Chemom.Intell.Lab.Syst.1997,39(1):11-18.
[23]刘春丽,刘满仓,朱彭龄.高效液相色谱法分析中药及植物药的进展.分析化学,2000,28(5):631-643
[24]Hayen H,Karst U,Strategies for the liquid chromatographic-mass spectrometric analysis of non-polar compounds.J.Chromatogr.A,2003,1000(1-2):549-565.
[25]Guetens G,De Boeck G,Wood M,Maes R A A,Eggermont A A M,Highley M S,van Oosterom A T,et.al.Hyphenated techniques in anticancer drug monitoring:I.Capillary gas chromatography-mass spectrometry.J.Chromatogr.A,2002,976(1-2):229-238.
[26]龚范,宋又群,彭源贵,梁逸曾,Leung A K M,Chau F T.平胃散中苍术挥发油的GC/MS分析,药学学报,2000,35(5):394-397.
[27]龚范,梁逸曾,宋又群,彭源贵,崔卉,Leung A K M,Chau F T.陈皮挥发油的气相色谱/质谱分析,分析化学2000,28(7):860-864.
[28]Gong F,Liang Y Z,Cui H,Chau F T,Chan B T P.Gas chromatography-mass spectrometry and chemometric resolution applied to the determination of essential oils in Cortex Cinnamomi.J.Chromatogr.A,2001,905(1-2):193-205.
[29]Gong F,Liang Y Z,Xu Q S,Chau F T.Determination of volatile components in peptic powder by gas chromatography-mass spectrometry and chemometric resolution.J.Chromatogr.A,2001,909(2)237-247.
[30]李晓宁,崔卉,宋又群,梁逸曾.辽五味子果实挥发油成分的鉴定.药学学报,2001,36(3):215-219.
[31]龚范,梁逸曾,宋又群,彭源贵,Leung A K M,Chau F T.平胃散挥发性成分的研究(Ⅱ)-厚朴挥发油的GC/MS分析.高等学校化学学报,2001,22(9):1481-1485.
[32]Li X N,LiangY Z.Analysis of the Volatile Fractions of Schisandra Chinensis (Turcz.)Baill.with GC/MS and Chemometric Resolution,Phytochemical Analysis,2003,14:23-33.
[33]Gong F,Liang Y Z.Combination of GC-MS with local resolution for determining volatile components from si-wu decoction,J.Seperation Science,2003,26:112-122.
[34]Li B Y,Hu Y,Liang Y Z,Huang L F,Xu C J,Xie P S.Spectral Correlative Chromatography and Its Application to Analysis of Chromatographic Fingerprints of Herbal Medicines.Journal of Separation Science,2004,27:581-588.
[35]Wang X S,Kapoor V,Smythe G A.Assessment of hydroxyl radical generation and radical scavenging activity of Chinese medicinal herbs using GC-MS.Am.J.Chin.Med,2003,31:927-944.
[36]Fu P P,Yang Y C,Xia Q S,Chou M W,Cui Y Y,Lin G.J.Mutagenic effects of aqueous extracts of Symphytum officinale L.and of its alkaloidal fractions.Food Drug Anal,2002,10(4):198-211.
[37]Tseng M C,Tsai M J,Lin J H,Wen K C H.GC/MS Analysis on Anorectics Adulterated in Traditional Chinese Medicines.J.Food Drug Anal.,2000,8(4):315-330.
[38]Vieira R F,Simon J E,Chemical characterization of Basil(Ocimum spp.)found in the markets and used in traditional medicine in Brazil.Econ.Bot.2002,54:207-216.
[39]Gherman C,Culea M,Cozar O.Comparative analysis of some active principles of herb plants by GC/MS.Talanta,2000,53:253-262.
[40]Velasco-Negueruela A,Perez-Alonso M J,Perez de Paz P L,J Pala-Paul,Sanz J.Analysis by gas chromatography-mass spectrometry of the essential oils from the aerial parts of Rutheopsis herbanica(Bolle)Hans.& Kunk.,gathered in Fuerteventura(Canary Islands).J.Chromatogr.A,2003,984(1):159-162.
[41]Velasco-Negueruela A,Perez-Alonso M J,Perez de Paz P L,Pala-Paul J,Sanz J.Analysis by gas chromatography-mass spectrometry of the essential oil from the aerial parts of Pimpinella junoniae Ceb.& Ort.,gathered in La Gomera,Canary Islands,Spain.J.Chromatogr.A,2003,1011(1-2):241-244.
[42]梁逸曾.白、灰、黑复杂多组分体系及其化学计量学算法.长沙:湖南科学技术出版社,1996
[43]俞汝勤.化学计量学导论.长沙:湖南教育出版社,1991.
[44]高鸿.分析化学现状与未来(“分析化学前沿”主题报告).北京:科学出版社,1991.
[45]国家自然科学基金会.自然科学学科发展战略调研报告.分析化学.北京:科学版社,1993.
[46]Malinowski E R.Factor analysis in chemistry(2~(nd)edition).Wiley,New York,1991.
[47]许禄.化学计量学方法.北京:科学出版社,1994.
[45]Maeder M.Evolving factor analysis for the resolution of overlapping chromatographic peaks.Anal.Chem.,1957,59:527-530
[49]Maeder M.,Zilian A.Evolving factor analysis,a new multivariate techniques in chromatography.Chemom.Intell.Lab.Syst.,1988,3:205-213
[50]Maeder M.,Zuberbuhler A D.The resolution of overlapping chromatographic peaks by evolving factor analysis.Anal.Chim.Acta,1956,181:287-291
[51]Kvalheim O.M.,Liang Y.Z.Heuristic evolving latent projections:resolving two-way multicomponent data.Part 1.Selectivity,latent projective graph,datascope,local rank and unique resolution.Anal.Chem.,1992,64:936-946
[52]Liang Y.Z.,Kvalheim O M,Keller H R,Massart D L,et al.Heuristic evolving latent projections:resolving two-way multicomponent data.Part 2:Detection and resolution of minor constituents.Anal.Chem.,1992,64:946-953
[53]Malinowski E.R.Window factor analysis,theoretic derivation and application to flow injection analysis data.J.Chemom.,1992,6,29-40
[54]Manne R.,Shen H.L.,Liang Y.Z.Subwindow factor analysis.Chemom.Intell.Lab.Syst.,1999,45:171-176
[55]Shen H L,Manne R.,Xu Q.S.,et al.Local resolution of hyphenated chromatographic data.Chemom.Intell.Lab.Syst.,1999,45:323-330
[56]沈海林,梁逸曾,俞汝勤,等.香港大气颗粒物中多环芳烃的HELP法解析.中国科学(B辑),1998,27:556-563
[57]Keller H.R.,Massart D.L..Peak purity control in liquid chromatography with photodiode-array detection by a fixed size moving window evolving factor analysis.Anal.Chim.Acta,1991,246:379-390
[58]Gong F.,Liang Y.Z.,Xu Q.S.,et al.Gas chromatography-mass spectrometry and chemometric resolution applied to the determination of essential oils in Cortex Cinnamomi.J.Chromatogr.A,2001,905:193-205
[59]Gong F.,Liang Y.Z.,Xu Q.S.,et al.Determination of volatile components in peptic powder by Gas chromatography-mass spectrometry and chemometric resolution.J.Chromato.A,2001,909:237-247
[60]Li X.N.,Cui H.,Song Y Q,et al.Analysis of the Volatile Fraction of Schisandra Chinensis(Turcz.)Baill.with GC/MS and Chemometric Resolution.Phytochemical Analysis.Phytochemical Analysis,2003,14:23-33
[61]龚范,梁逸曾,宋又群,等.平胃散挥发性成分的研究(Ⅱ)-厚朴挥发油的GC/MS分析.高等学校化学学报,2001,22(9):1481-1485
[62]亓云鹏,孙胜利,吴玉田,等.直观推导式演进特征投影法测定不同方法提取的国产血竭中龙血素B的含量.分析化学,2002,30(7):797-800
[63]江苏新医学院.中药大辞典,上海:上海大众出版社,2003.
[64]王丹丹,刘盛泉,陈英杰,等.紫丁香有效成分的研究.药学学报,1982,17(12):951-954
[65]薛俊玲,腾慧梅.甲丁胶囊的抗病毒实验研究.中医药信息,1997,2:47
[66]Yan X.J.,Zhou J.J.,Xie G.R.,et al."Traditional Chinese Medicines:Molecular Structures,Natural Sources and Applications",Aldershot,Ashgate,1999
[67]Wagner C.,Sefkow M.,Kopka.Construction and application of a mass spectral and retention time index database generated from plant GC/EI-TOF-MS metabolite profiles.Phytochemistry,2003,62:887-900
[68].Kovats E.Sz.,Gas-chromatographische Charakterisierung organischer Verbindungen.Teil 1:Retentions indices aliphatischer Halogenide,Alkohole, Aldehyde und Ketone.Helv.Chim.Acta,1958,41:1915-1929
[69]Wang Y.H.,Wong EK.Mathematical relationships between vapor pressure,water solubility,Henry's law constant,n-octanol/water partition coefficent and gas chromatographic retention index of polychlorinated-dibenzo-dioxins.Water Research,2002,36:350-355
[70]H.van Den Dool and E Dec.Kratz.A generalization of the retention index system including linear temperature programmed gas—liquid partition chromatography.J.Chromatogr.,1963,11:463-471
[71]Manne R.,Shen H.L.,Liang Y.Z.Subwindow factor analysis.Chemom.Intell.Lab.Syst.,1999,45:171-176
[72]Li B.Y.,Hu Y.,Liang Y.Z.,et al.Spectral Correlative Chromatography and Its Application to Analysis of Chromatographic Fingerprints of Herbal Medicines.J.Separation Science,2004,27:581-588
[73]刘正信,高海翔,郑培清,等.粉绿铁线莲挥发油成分分析.天然产物研究与开发,2001,13(5)25-27
[74]Kvalheim O.M.,Liang Y.Z.Heuristic evolving latent projections:resolving two-way multicomponent data.Part 1.Selectivity,latent projective graph,dataseope,local rank and unique resolution.Anal.Chem.,1992,64:936-946
[75]赵晨曦,梁逸曾.公丁香与母丁香挥发油化学成分的Gc/MS研究,中药现代实践.2004,18:92-95
[81]金国琴,赵伟康.首乌制剂对老年大鼠胸腺、肝脏蛋白质和核酸含量的影响,中草药.1994,25(11):590-591.
[82]应久皓,周学优,朱秀琴.何首乌炮制品药理临床研究.中国中药杂志.1992,17(12):722-724.
[83]魏锡云,张锦堃,罗映辉,等.黄芪和何首乌抗环磷酰胺诱导胸腺细胞凋亡.中国药科大学学报.2000,31(1):35-38.
[84]黄运忠,张树秋,李民,等.乌提取液对小白鼠HDL中胆固醇含量的影响.右江民族医学院学报.1990,12(4):8-10.
[85]段江燕,张金红,许乃寒,等.首乌复方对兔红细胞膜Ca~(2+),Mg~(2+)-ATPase 活性的影响.中草药.2000,31(8):613-614.
[86]徐萃华,李燕娜.何首乌对体外培养肝细胞(7-~3H)-胆固醇掺入的影响.中医药学报.1987,(3):39-40.
[87]吴兆洪,杨永华,刘玉瑾,等.首乌冲剂改善高脂血症与高凝状态的临床观察.中成药.2000,2(12):844-846.
[88]叶定江,朱荃,祁辉林,等.何首乌及其炮制品的免疫药理学研究.中药通报.1987,12(3):21-24.
[89]姚鸣春,罗碧如,蓝开蔚,等.中药何首乌抗衰老作用的研究.药学通报.1984,19(11):28-30.
[90]杨秀伟.何首乌醇提物对易老化小鼠肝脏和脑单胺氧化酶活性的影响.中国中药杂志.1996,21(1):48-49.
[91]胥庆华,刘丽云,赵瑞华,等著.中药药对大全.北京:中国中医药出版社,2004.67-68
[92]鲁佳慧,江滨,曾元儿,等.中药配伍的研究进展.时珍国医国药,2003,14(7):419-421
[93]李晓如,梁逸曾等,中药药对的化学成分研究川芎.赤芍挥发油的GC-MS 分析.高等学校化学学报,2006,(2007);443-448
[94]何佳霞,蒋盂良,冯映冰,等.芍药汤配伍的化学变化研究.中国中药杂志,1998,23(7):432-434
[95]徐艳春,魏璐雪,周玉新,等.高效液相法测定黄连与吴茱萸配伍前后吴茱萸碱及吴茱萸次碱的含量.中国中药杂志,2001,26(12):846-849
[96]黄熙,任平,王骊丽,等.不同煎煮方法和配伍因素对汤剂中阿魏酸含量的影响.中草药,2001,32(5):41-45
[97]涂瑶生,刘法锦,孙冬梅,等.清胃散单煎与合煎中盐酸小檗碱含量的测定.中国中医基础医学杂志,2000,6(8):531-533
[98]袁久荣.四物汤的实验研究.中国中药杂志,1999,16(3):153-155
[99]曾慧芳,苏子仁,史俏蓉,等.虎杖单煎、复方共煎过程中的物理化学变化初探.中国药房,1999,10(3):112-113
[100]容蓉,袁久荣.四物汤及其配伍组方中苯甲酸煎出量的HPLC法测定.中草药,2001,32(2):114-115
[101]张宇,陈丽艳,杨义,等.四逆汤口服液中附子与甘草配伍前后有效成分变化.佳木斯医学院学报,1996,19(1):27-30
[102]崔健,耿惠,刘淑杰,等.山豆根在复方中化学成分变化的研究.中草药,2001,32(7):613-614
[103]夏云,李志明,朱丹妮,等.生脉散复方化学动态变化与药效关系的研究.中国中药杂志,1998,23(4):230-231
[104]涂瑶生,刘法锦,孙冬梅,等.单味中药浓缩颗粒组成的三利降脂方与煎提取物的化学成分比较.中药新药与临床药理,1998,9(2):108-120
[105]张志伟.汤剂合煎与分煎混合所得成分之初探.中成药研究,1986,7(4): 41-42
[106]谭洪根,刘应泉,冯维秀,等.芍药甘草汤配伍的化学成分研究.中国中药杂志,1995,20(9):550-551
[107]陈建萍,吴伟康,张敏生,等.中药复方配伍规律研究的思路与方法.中国实验方剂学杂志,2000,6(1):1-4
[108]王庆国,韩学杰,李成为.冠心病临床药对新用.中国医药科技出版社.2005
[109]Kvalheim O M,Liang Y Z.Heuristic evolving latent projections-resolving 2-way multicomponent data.1.Selectivity,latent-projective graph,datascope,local rank and unique resoltuion.Anal.Chem.1992,64(8):936-946.
[110]Liang Y Z,Kvalheim O M,Keller H R,et.al.Heuristic evolving latent projections- Resolving 2-way multicomponent data.2.Detection and resolution of minor constituents.Anal.Chem.,1992,64(8):946-953.
[111]Cheng Y Y,Chen M J,Tong W D.An Approach of comparative analysis of Chromatographic Fingerprints for Assuring the Quality of Botanical Drugs.J.Chem.Inf.Comput.Sci.,2003,43:1068-1076
[112]梁逸曾,谢培山.指纹图谱的化学模式识别分析-若干实质性问题的探讨.世界科学技术-中药现代化,2002,4(5):47-51
[113]Cheng Y Y,Chen M J,Tong W D.An Approach of comparative analysis of Chromatographic Fingerprints for Assuring the Quality of Botanical Drugs.J.Chem.Inf.Comput.Sci.,2003,43:1068-1076
[114]Woo Y H,Kim H J,Cho J H.Identifivation of herbal medicines using recognition techniquesWith near-infrared reflectance.Microchemical Joural,1999,63:61-70
[115]陈念贻,钦佩,陈瑞亮等.模式识别方法在化学化工中的应用.北京:科学出版社,2000
[116]Welsh W J,Lin W,Terignl S H,et al.Pharmaceutical fingerprinting:Evaluation of neural networks and chemometric techniques for distinguishing among same-product manufractures.Anal.Chem.1996,68:3473-3482
[117]屈凌波,相柄仁,安登奎.人工神经网络在中药模式识别中的应用.计算机与应用化学,200,19(4):428-431
[118]罗旭,毕开顺,王玺等.中药质量化学模式识别研究进展.药学学报,1993,28(12):936-940
[119]Wold H.Estimation of principal components and related models by iterative least squares.In:Krishnaiah P R,eds.Multiuariate analysis.New York: Academic Press, 1966. 391-420.
[120] Jong de S. SIMPLS: an alternative approach squares regression. Chemometrics and Intelligent Laboratory Systems, 1993,18 (3): 251-263.
[121] Brown C W, Lynch P F, Obremski R J, et al. Matrix representations and criteria for selecting analytical wavelengths for multicomponent spectroscopic analysis. Analytical Chemistry, 1982,54(9): 1472-1479.
[122] Kisner H J, Brown C W, Kavarnos G J. Multiple analytical frequencies and standards for the least-squares spectrometric analysis of serum lipids. Analytical Chemistry, 1983,55(11): 1703-1707.
[123] Golub G, Kalian W. Calculating the singular values and pseudo-inverse of a matrix. Journal of the Society for Industrial and Applied Mathematics: Series B, Numerical Analysis, 1965,2(2):205-224.