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Hildebert Wagner · Rudolf Bauer · Dieter MelchartPei-Gen Xiao · Anton StaudingerEditors

Chromatographic FingerprintAnalysis of Herbal Medicines

Thin-layer and High Performance Liquid Chromatography of Chinese Drugs

Second, Revised and Enlarged Edition

Vol. 1

Editors

Prof.em.Dr.Dr.h.c.mult. Hildebert WagnerLudwig-Maximilians-UniversityCenter of Pharma ResearchDepartment PharmacyGermany, Munich

Prof. Dr. Rudolf BauerKarl-Franzens-University GrazInstitute of Pharmaceutical ScienceDepartment of PharmacognosyAustria, Graz

Univ.-Prof. Dr. med. Dieter MelchartCompentence Centre for Complementary Medicine and NaturopathyTechnical University MunichGermany, Munich

Prof. Pei-Gen XiaoThe Editorial Offi ce of Chinese Herbal Medicine, BeijingInstitute of Medicinal Plant DevelopmentChinese Academy of Medical SciencesBeijing, China

Dipl.Kfm. Anton StaudingerVisiting Professor at Beijing University of Chinese MedicineExecutive Council Member of WFCMSTCM hospital Bad Kötzting, First German hospital of Traditional Chinese MedicineHospital for Psychosomatically and PsychotherapeuticallyGeneral Manager Bad Kötzting, Germany

Printed with fi nancial support of TCM-Klinik Bad Kötzting, Germany

“Chinese Drug Monographs and Analysis” originally published by Verlag für Ganzheitliche Medizin, Dr. Erich Wühr GmbH, © 2004

This work is subject to copyright.All rights are reserved, whether the whole or part of the material is concerned, specifi cally those of translation, reprinting, re-use of illustra-tions, broadcasting, reproduction by photocopying machines or similar means, and storage in data banks.

Product Liability: The publisher can give no guarantee for all the information contained in this book. This does also refer to information about drug dosage and application thereof. In every individual case the respective user must check its accuracy by consulting other phar-maceutical literature.

The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specifi c statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

© 2011 Springer-Verlag/Wien

SpringerWienNewYork is part of Springer Science+Business Mediaspringer.at

Photocredits:© Cover illustration and all fi gures with courtesy of the editors and authors

Coverdesign: WMXDesign GmbH, Heidelberg, GermanyTypesetting: Thomson Press (India) Ltd., Chennai, India

Printed on acid-free and chlorine-free bleached paperSPIN: 80025669

With 376 (partly coloured) fi gures

Library of Congress Control Number. 2011926593

ISBN 978-3-7091-0762-1 SpringerWienNewYork

v

Editorial

On the occasion of the twentieth anniversary of the establishment of the rst hospital of Traditional Chinese Medicine (TCM) in Germany, the editors are pleased to present a new analytical manual for the quality proof of Chinese herbal drugs that meets the high standards of the European Drug Regulatory Authority.

The chromatographic TLC-, HPLC- and GC- ngerprint analytical technique described in the monographs has never been used in any Pharmacopoeia, although it is the most comprehensive, non-sophisticated chromatographic method for a science-based identity and stability proof of Chinese Herbal Drugs and includes the detection of possible falsi cations or adulterations. This ngerprint analysis enables, for the rst time, the detection of the complex entities of all main

low-molecular constituents of a plant drug with the advantage that the single constituents can be made visible in coloured TLC photographs and HPLC-peak pro les. Using online recordable UV-spectra with the Diode Array technique, it is also possible to gain information about the chemical structure of single constituents.

Each new monograph also contains a description of the macroscopic descriptions, an updated list of all the main bioactive constituents of a drug identi ed to date, and the pharmacological and biological activities of the single herbal drugs and their therapeutic application. A comprehensive reference list informs the reader about new analytical topics and trends.The eighty individual herbal drug monographs were rst published by Dr. Wühr Publishers,Bad Kötzting and are now offered in an updated and corrected form in this new, two-volume manual published by Springer Publishing Company. A third volume containing further 40 herbal drug monographs will be completed by the end of 2012.

Scienti c experts from the Universities of Munich (Germany) and Graz (Austria), along with around 25 scienti c co-workers and technicians, contributed to this comprehensive work. All participants in the project are most grateful to the owner of the TCM-hospital Bad Kötzting who has supported the project from its very beginning. In the later phases of the project, we also received nancial support from the AiF-program of the German Ministry of Economics in Berlin (Germany).

The editors: H. Wagner, R. Bauer, D. Melchart, Xiao Pei-Gen, A. StaudingerApril 2011

vii

Table of Contents

Vol. I: Monographs No. 1 – 40Vol. II: Monographs No. 41 – 80

Table of Contents Vol. I

Contents alphabetically (lat. names) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiContents alphabetically (chin. names) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvAcknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xixIntroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxiPractical work guidelines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxv

TCM-Analytical Monographs Vol. I

1. Bupleuri, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12. Frittilariae, Bulbus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133. Rehmanniae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234. Schisandrae, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375. Asari, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456. Houttuyniae cordatae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597. Pinelliae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 718. Astragali, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839. Angelicae pubescentis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9910. Atractylodis macrocephalae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11311. Belamcandae sinensis, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12712. Lycopi lucidi, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14113. Notopterygii, Rhizoma seu Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15114. Angelicae sinensis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16115. Angelicae dahuricae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17116. Ligustici chuanxiong, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18117. Zanthoxyli, Pericarpium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19118. Magnoliae offi cinalis, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20319. Drynariae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21120. Puerariae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22121. Codonopsis pilosulae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23322. Gardeniae, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24523. Gastrodiae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25524. Ecliptae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26325. Andrographis, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27326. Paeoniae albae/rubrae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

Contents Vol. I

viii

27. Sophorae, Flos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29128. Coptidis, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30129. Stephaniae tetrandrae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31130. Ziziphi spinosae, Semen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32531. Amomi rotundus, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33532. Uncariae cum Uncis, Ramulus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34333. Clematidis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35534. Sinomenii, Caulis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36935. Forsythiae, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38136. Evodiae, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39137. Anemarrhenae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40338. Acanthopanacis senticosi, Radix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41539. Scrophulariae, Radix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42740. Polygoni multifl ori, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439

Appendix:Basic Solvent Systems, reagents and columns for the TLC-, GC- and HPLC-fi ngerprint Analysis of main structure types of natural products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457Drug monograph, Marker compounds, Chemical classifi cation, Processing . . . . . . . . . . . . . 461

ix

Contents Vol. II

Table of Contents Vol. II

Vol. I: Monographs No. 1 – 40Vol. II: Monographs No. 41 – 80

TCM-Analytical Monographs Vol. II

41 Alismatis, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46742 Carthami, Flos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47543 Epimedii, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48544 Cnidii, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49945 Lycii radicis, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50946 Lycii, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52147 Mori radicis, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53548 Mori, Folium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54949 Cimicifugae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55950 Phellodendri amurensis, Cortex Phellodendri chinensis, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57351 Lonicerae, Flos Lonicerae japonicae, Flos Lonicerae japonicae, Caulis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58752 Curcumae, Radix Curcumae longae, Rhizoma Curcumae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601 53 Dioscoreae oppositae, Rhizoma Dioscoreae hypoglaucae, Rhizoma Dioscoreae nipponicae, Rhizoma Dioscoreae septemlobae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61554 Ganoderma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63355 Citri reticulatea, Pericarpium Citri reticulatea viride, Pericarpium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647 56 Corydalis, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66557 Dipsaci, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67758 Atractylodis lanceae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69159 Leonuri, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70760 Magnoliae, Flos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71961 Piperis longi, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72962 Sophorae fl avescentis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74363 Scutellariae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75564 Chaenomelis, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76765 Acori calami, Rhizoma Acori tatarinowii, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77766 Isatidis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79167 Tribuli, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805

Contents Vol. II

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68 Ophiopogonis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81969 Eucommiae, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83170 Notoginseng, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84371 Rhei, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85772 Ginseng, Radix et Rhizoma Panacis Quinquefolii, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87573 Siegesbeckiae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89374 Salviae miltiorrhizae, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90375 Poria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92376 Cassiae, Semen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93577 Camelliae, Folium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95178 Artemisiae Scopariae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96779 Aconiti lateralis praeparata, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977 Aconiti kusnezoffi i praeparata, Radix 80 Cinnamomi, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991

Appendix:Basic Solvent Systems, reagents and columns for the TLC-, GC- and HPLC-fi ngerprint Analysis of main structure types of natural products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1009Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015Drug monograph, Marker compounds, Chemical classifi cation, Processing . . . . . . . . . . . . . 1019

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Contents alphabetically

lat. name chapter volume pageAcanthopanacis senticosus 38 I 415Aconitum kusnezo i 79 II 977Aconitum lateralis 79 II 977Acorus calamus 65 II 777Acorus tatarinowii 65 II 777Alisma orientalis 41 II 467Amomum compactum 31 I 335Amomum kravanh 31 I 335Amomum longiligulare 31 I 335Amomum villosum 31 I 335Amomum xanthioides 31 I 335Andrographis paniculata 25 I 273Anemarrhenae asphodeloides 37 I 403Angelica biserrata 9 I 99Angelica dahurica 15 I 171Angelica formosana 15 I 171Angelica pubescens 9 I 99Angelica sinensis 14 I 161Artemisia capillaris 78 II 967Artemisia scoparia 78 II 967Asarum heterotroppoides 5 I 45Asarum mandshuricum 5 I 45Asarum seoulense 5 I 45Asarum sieboldii 5 I 45Astragalus chrysopterus 8 I 83Astragalus oridus 8 I 83Astragalus membranaceus 8 I 83Astragalus mongholicus 8 I 83Astragalus tongolensis 8 I 83Atractylodes chinensis 58 II 691Atractylodes lanceae 58 II 691Atractylodes macrocephala 10 I 113Belamcanda sinensis 11 I 127Bupleurum chinense 1 I 1Bupleurum scorzonerifolium 1 I 1Camellia sinensis 77 II 951Carthamus tinctorius 42 II 475Cassia obtusifolia 76 II 935Cassia tora 76 II 935

Contents alphabetically

xii

Chaenomeles speciosa 64 II 767Cimicifuga dahurica 49 II 559Cimicifuga heracleifolia 49 II 559Cimicifuga racemosa 49 II 559Cimicufuga foetida 49 II 559Cinnamomum cassia 80 II 991Cinnamomum ceylanicum 80 II 991Citrus reticulata 55 II 647Citrus reticulata viride 55 II 647Clematidis chinensis 33 I 355Clematidis hexapetala 33 I 355Clematidis manschurica 33 I 355Cnidium monnieri 44 II 499Codonopsis modesta 21 I 233Codonopsis pilosula 21 I 233Codonopsis tangshen 21 I 233Coptis chinensis 28 I 301Coptis deltoides 28 I 301Coptis teeta 28 I 301Corydalis yanhusuo 56 II 665Curcuma kwangsiensis 52 II 601Curcuma longa 52 II 601Curcuma phaeocaulis 52 II 601Curcuma wenyujin 52 II 601Curcuma xanthorrhiza 52 II 601Dioscorea futschauensis 53 II 615Dioscorea hypoglauca 53 II 615Dioscorea nipponica 53 II 615Dioscorea opposita 53 II 615Dioscorea septemloba 53 II 615Dipsacus asperoides 57 II 677Drynaria fortunei 19 I 211Eclipta prostrata 24 I 263Epimedium acuminatum 43 II 485Epimedium brevicornum 43 II 485Epimedium koreanum 43 II 485Epimedium pubescens 43 II 485Epimedium sagittatum 43 II 485Epimedium wushanense 43 II 485Eucommia ulmoides 69 II 831Evodia bodineiri 36 I 391Evodia of cinalis 36 I 391Evodia rutaecarpa 36 I 391

xiii

Contents alphabetically

Forsythia suspensa 35 I 381Frittilaria cirrhosa 2 I 13Frittilaria delavayi 2 I 13Frittilaria hupehensis 2 I 13Frittilaria pallidi ora 2 I 13Frittilaria przewalskii 2 I 13Frittilaria thunbergii 2 I 13Frittilaria unibraceteata 2 I 13Frittilaria ussuriensis 2 I 13Frittilaria verticillata 2 I 13Frittilaria walujewii 2 I 13Ganoderma lucidum 54 II 633Ganoderma sinensis 54 II 633Gardenia jasminoides 22 I 245Gastrodia elata 23 I 255Houttuynia cordata 6 I 59Isatis indigotica 66 II 791Leonurus japonicus 59 II 707Ligusticum chuanxiong 16 I 181Lonicera confusa 51 II 587Lonicera hypoglauca 51 II 587Lonicera japonica 51 II 587Lonicera marcanthoides 51 II 587Lycium barbarum 45/46 II 509/521Lycium chinense 45/46 II 509/521Lycopus lucidus 12 I 141Magnolia biloba 18 I 203Magnolia biondii 60 II 719Magnolia denudata 60 II 719Magnolia lilii ora 60 II 719Magnolia of cinalis 18 I 203Magnolia sprengeri 60 II 719Morus alba 47/48 II 535/549Notopterygium forbesii 13 I 151Notopterygium incisum 13 I 151Ophiopogon japonicus 68 II 819Paeonia lacti ora 26 I 281Paeonia veitchii 26 I 281Panax ginseng 72 II 875Panax notoginseng 70 II 843Panax quinquefolium 72 II 875Phellodendron amurense 50 II 573Phellodendron chinensis 50 II 573

Contents alphabetically

xiv

Pinellia ternata 7 I 71Piper longum 61 II 729Polygonum multi orum 40 I 457Poria cocos 75 II 923Pueraria lobata 20 I 221Rehmannia glutinosa 3 I 23Rehmannia hueichingensis 3 I 23Rehmannia lutea 3 I 23Rehmannia purpurea 3 I 23Rheum of cinale 71 II 857Rheum palmatum 71 II 857Rheum tanguticum 71 II 857Salvia miltiorrhiza 74 II 903Schisandra chinensis 4 I 37Scrophularia ningpoensis 39 I 427Scutellaria baicalensis 63 II 455Siegesbeckia glabrescens 73 II 893Siegesbeckia orientalis 73 II 893Siegesbeckia pubescens 73 II 893Sinomenium acutum 34 I 369Sinomenium cinerum 34 I 369Sophora avescens 27 I 291Sophora japonica 27 I 291Stephania tetrandra 29 I 311Tribulus terrestris 67 II 805Uncaria hirsuta 32 I 343Uncaria macrophylla 32 I 343Uncaria rhynchophylla 32 I 343Uncaria sessilifructus 32 I 343Uncaria sinensis 32 I 343Uncaria tomentosa 32 I 343Zanthoxylum armatum 17 I 191Zanthoxylum bungeanum 17 I 191Zanthoxylum piperitum 17 I 191Zanthoxylum schinifolium 17 I 191Ziziphus jujuba 30 I 325

xv

Contents alphabetically

chin. name Chapter volume pageBaishao 26 I 281Baizhi 15 I 171Baizhu 10 I 113Banlangen 66 II 791Banxia 7 I 71Beimu 2 I 13Bibo 61 II 729Cangzhu 58 II 691Chaihu 1 I 1Cha-yeh 77 II 951Chenpi 55 II 647Chishao 26 I 281Chuanshanlong 53 II 615Chuanxinlian 25 I 273Chuanxiong 16 I 181Ciwujia 38 I 181Dahuang 71 II 857Danggui 14 I 161Dangshen 21 I 233Danshen 74 II 903Digupi 45 II 509Dihuang 3 I 23Duhuo 9 I 99Duzhong 69 II 831Ezhu 52 II 601Fangji 29 I 311Fenbixie 53 II 615Fuling 75 II 923Fuzi 79 II 977Gegen 20 I 221Gouqizi 46 II 521Gouteng 32 I 343Guanhuangbo 50 II 573Gusuibu 19 I 211Heshouwu 40 I 439Honghuo 42 II 475Houpo 18 I 203Huaihua 27 I 291Huaimi 27 I 291Huajiao 17 I 191

Contents alphabetically

xvi

Huangbo 50 II 573Huanglian 28 I 301Huangqi 8 I 83Huangqin 63 II 755Jianghuang 52 II 601Jili 67 II 805Jinyinhua 51 II 587Juemingzi 76 II 935Kushen 62 II 743Lianqiao 35 I 381Lingzhi 54 II 633Maidong 68 II 819Mianbixie 53 II 615Mohanlian 24 I 263Mugua 64 II 767Qianghuo 13 I 151Qingfengteng 34 I 369Qingpi 55 II 647Rendongteng 51 II 587Renshen 72 II 875Rougui 80 II 991Sangbaipi 47 II 535Sangye 48 II 549Sanqi 70 II 843Shanyao 53 II 615Shanyinhua 51 II 587Sharen 31 I 335Shechuangzi 44 II 499Shegan 11 I 127Shengma 49 II 559Shichangpu 65 II 777Suanzaoren 30 I 325Tianma 23 I 255Weilingxian 33 I 355Wuweizi 4 I 37Wuzhuyu 36 I 391Xinyi 60 II 719Xixiancao 73 II 893Xixin 5 I 45Xiyangshen 72 II 875Xuaanshen 39 I 427

xvii

Contents alphabetically

Xuduan 57 II 677Yanhusuo 56 II 665Yimucae 59 II 707Yinchen 78 II 967Yinyanghuo 43 II 485Yujin 52 II 601Yuxingxao 6 I 59Zelan 12 I 141Zexie 41 II 467Zhangchangpu 65 II 777Zhicaowu 79 II 977Zhimu 37 I 403Zhizi 22 I 245

xix

Acknowledgements

The editors wish to express their deep gratitude to the TCM-Hospital Bad KötztingA. Staudinger and the Federal Ministry for Economics and Technology (AiF) Berlin, Germany for nancial support as well as to CEO Biol. Chem. H. Rausch, Phytochem Reference substances, Ichenhausen/Neu Ulm, Prof. A. Vollmar, LMU Munich, Department of Pharmacy, and Prof. F. Bracher, LMU Munich for their cooperation in the development of the Chinese Herbal Monographs. We also thank Prof. Dai Jingzhang TCM-Hospital Bad Kötzting/Beijing, University of Chinese Medicine and Dr. C-H. Hempen, Center of Chinese Medicine Munich for their valuable explanation of the standard therapy using Chinese drugs.

We are deeply indebted our many scienti c coworkers and colleagues at the University of Munich (Germany) and the University of Graz (Austria), as well as to the Technical Assistants of the Department of Pharmacy, Munich named following:

Department of Pharmacy Munich, Scienti c Assistants: Bauer Michael, Fischer Mathilde, Liu Yong, Michler Hans, Müller-Jakic Barbara, Nenninger Anneli, Nörr Heidrun, Offermann Franziska, Plößl Florian, Pröbstle Andrea, Wild Bernice, Zschocke Sibylle. Technical Assistants: Bächer Silvia, Grieblinger Elisabeth, Koch Stefanie, Marotel Dana, Mayr Christine.

Pharmacognosy University Graz: Adams Michael, Lehmann Reg, Liu Jianghua, Reininger Eveline, Resch Marion Sylvia, Schühly Wolfgang Martin, Schwarte Anne, Seibt Anette, Stöhr Jochen.

The editors gratefully acknowledge the excellent cooperation with the Springer Publ. Comp. and Mrs. Dr. Claudia Panuschka and Mrs. Angelika Heller in particular.

xxi

Introduction

Facts and Perspectives on Chinese Herbal Drugs

When we began our work on the new analytical monographs 15 years ago, we faced the challenge of how the quality proof should be performed in order to meet both the requirements of a science-based authenticity proof of the Chinese drugs and the high standards of the European Drug Regulatory Authority. Based on the experience we had gained from our fi rst TLC-fi ngerprinting of herbal drugs (Wagner and Bladt 2001), we decided to use the chromatographic TLC and HPLC fi ngerprint analytical technique. This method enables the researcher, for the fi rst time, to detect the complex entities of all main low molecular constituents of a plant drug, with the advantage that the single constituents can be made visible in coloured TLC photographs and in a quantifi able HPLC-peak profi ling. At the same time, for safety reasons, these new techniques can be used to exclude possible falsifi cations and adulterations of herbal drugs. These criteria and advantages have also persuaded the Chinese scientifi c experts who advocated this analytical method as the best, presently available, non-sophisticated and feasible method for quality proof of herbal drugs (Liang et al. 2010). The fi ngerprint technology for identifi cation of herbal drugs is also the favored method in the framework of the international ISO-Standardisation* of the “Quality and Safety of TCM”. If the barcode DNA-analysis of all frequently used Chinese drugs becomes available in the near future, we can supplement and correlate the chromatographic analyses with those of the DNA-fi ngerprint analyses and thereby optimize the quality proof of the drugs in general (Heubl 2010).

Authenticity of TCM-drugs not defi nitely assessedMany TCM herbal drugs are not yet produced under controlled cultivations, but originate from wild collections. Even if the drugs are derived from cultivations, it must be taken into account that they can originate from quite varied climate zones and that they may be harvested under altered conditions. Therefore, in the past, the botanical authenticity and homogeneity within a defi ned plant species could not be guaranteed. We have thus investigated as many herbal drug samples of one plant species as we were able to acquire from different districts and markets in China, along with reference drugs from German herbal drug fi rms (Wagner et al. 2011).

Uncertain botanical nomenclature The non-uniform nomenclature for the same plant in various regions of China is

a signifi cant problem. This uncertainty can cause impermissible substitutions or falsifi cations, as occurred 15 years ago when the root of Stephania tetrandra (Hanfangji) was mistaken for the root of Aristolochia fangji (Guanfangji) and administered to women

*Resolution 18 of the 2nd plenary meeting of ISO/TC 249 held in The Haque, Netherlands on May 2-4th 2011 [Establishment of the working group “Quality and Safety of TCM products” under german convenorship] www.iso.org and www.din.de

Introduction

xxii

as tea medication that produced severe nephrotoxic side effects. The Aristolochia herbal drug contains the carcinogenic aristolochic acid. After the detection of this falsifi cation, the drug was banned from the Chinese Pharmacopoeia in 2002. Meanwhile, special TLC- and HPLC-fi ngerprint methods were developed which allow the detection of even micrograms of these acids in an herbal drug or drug mixtures: see Radix Stephaniae p. 311 Mo. No. 29, Radix Clematidis p. 355 Mo. No. 33 and Caulis Sinomenii p. 369 Mo. No. 34. A similar example is the Chinese tetraploid Acorus calamus/tatarinowii drug, Mo. No. 65 p. 777, which differs in its very high content of carcinogenic ß-asarone from the diploid Acorus calamus drug known offi cially in most western countries.

Great variability of plant speciesA further diffi culty in the identifi cation of TCM-drugs is the fact that, in many Chinese monographs, more than 2 species or subspecies (sometimes up to 9 species) are listed and are often labelled as synonyms, subspecies or subvarieties. For example in Fritillariae bulbus Mo. No. 2 p. 13, nine species are listed, and the monographs for Epimedii herba-Mo. No. 43 p. 485, Dioscoreae rhizoma Mo. No. 53 p. 615 and Uncariae ramulus c. uncis Mo. No. 32 p. 343 list fi ve species each without any evidence that the chemical composition of the various “species” are qualitatively and/or quantitatively equivalent and can be substituted for one another. As a result of our fi ngerprinting investigations, we could show that in many cases considerable differences were detectable between the single species and the main offi cial herbal drug. Correspondingly it may be suggested that a great number of these “subspecies” do not possess pharmacological and therapeutic equivalence.

Conclusion: What have we learned from the authenticity proof of Chinese herbal drugs?In addition to a continuation of further pharmacological and molecular-biological investigations, we must immediately initiate comprehensive bar-code DNA-fi ngerprint analyses of the most frequently used offi cial Chinese plant drugs. The fi rst priority should be given to those Chinese plants within taxa that are frequently substituted or adulterated with other species and could be nearly indistinguishable morphologically or chemically (see herbal drugs of the Apiaceae familiy Mo. No. 9, 14, 15, 16, 44).

Processing of TCM-drugsApart from the simple cutting and cleaning of the raw drugs, the Chinese Pharmacopoeia describes many other types of pre-treatment or processing unknown to western Pharmacopoeias. In the Chinese Pharmacopoeia 2005 (People’s Republic of China, English Edition Vol I Appendix II A – 24) the processing is to be defi ned “to fulfi l the requirements of drugs”, whatever that may mean for each single drug. In one recent publication, the purpose of processing is explained as “to alter the appearance, the physical characteristics and chemical constituents of a herbal drug” (see Zhao Z et al. 2010). In none of the monographs, however those crude drugs containing toxic constituents, the necessity of the various processing is rationalized and clearly substantiated. According to the Chinese Pharmacopoeia, processing can be achieved primarily through the following methods: roasting and broiling, scalding, calcining, carbonizing, steaming, boiling, stewing, processing with wine, vinegar, or salt water, and different kinds of stir baking. Some chemicals or herbal drugs may also be used for the processing.

In the Monograph No. 79 p. 977, we describe a TLC- and HPLC-fi ngerprint analysis of two unprocessed (non-pretreated) and processed Aconitum spp., Aconitum carmichaeli

xxiii

Introduction

and Aconitum kusnezoffi i. Processing was performed, according to the “Heishunpian” and “Baifupian” instructions of the Chinese Pharmacopoeia, with salted water and Radix Glycyrrhizae, black beans and water or after scalding by heating at high temperature with sand (clamshell or talc). The TLC- and HPLC-fi ngerprint analyses showed that in the processed roots, the alkaloids Aconitine and Mesaconitine were degraded to a great extent and detectable only in a very small amount as compared with the content of these alkaloids in the raw unprocessed roots. Another herbal drug which requires processing is Rhizoma Pinelliae (Mo. No. 7 p. 71) which is not permitted to be prescribed in unprocessed form for oral therapy.

Conclusion: Modern analytical techniques using the HPLC-quantitation should replace the classical methods of processing described in the Chinese Pharmacopoeia. Recent publications demand a safe limit to be stipulated for the Aconitine content in processed Aconitum drugs (Singhuber et al. 2009).

Endo (Phyto) Fungi in Chinese HerbsDuring the development of the new monographs, we discovered a conspicuous occurrence of very lipophilic acetylenic compounds of the Falcarin(di)ol type in the roots of three Angelica spp. (Mo. No. 9, 14 and 15 p. 99, 161 and 171), in the root of Ligusticum chuanxiong (Mo. No. 16 p. 181) and in three Panax spp. (Mo. No. 70, 72 p. 843, 875). Initially, we considered them to be constituents biosynthesized from the plants. Meanwhile, however, several publications appeared in which the original production of these compounds from endo(phyto)fungi in Chinese plants could be assessed (Strobel and Daisy 2003; Li et al. 2007). The most famous example of the production of a long-known terpene alkaloid. by an endo(phyto) fungus is the Taxus brevifolia tree, the bark of which contains the symbiotic living fungus Taxomyces andreanae. This fungus is able to biosynthesize the same terpene alkaloid, paclitaxel, as the Taxus tree (Stierle et al. 1993). Which organism, the fungus or the plant, fi rst produced paclitaxel and was the gene supplier for the other organism is not known. The acetylene compounds falcarinols possess antibiotic and antitumoral activity. They are very lipophilic and can be easily detected because of their very characteristic UV-spectra. Therefore they are of interest for the “identity proof” of a plant and it can also be suggested that they contribute to the pharmacological and therapeutic effect of some Chinese plants containing these compounds. It can be expected that in the future, additional metabolites produced by phytofungi will be detected. There is no doubt that this surprising new knowledge will initiate a promising new area of research.

References

Chinese Pharmacopoeia of the People’s Republic of China, English Edition 2005 Vol I. Appendix II A – 24.

Heubl G (2010): New Aspects of DNA-based Authentication of Chinese Medicinal Plants by Molecular Biological Techniques, Planta Med. 76: 1963-1974.

Liang Y-Z, Xie P, Chan R (2010): Perspective of Chemical Fingerprinting of Chinese Herbs, Planta Med. 76: 1997-2003.

Li WC, Zhou J, Guo SY, Guo LD (2007): Endophytic fungi associated with lichens in Baihua mountain of Beijing, China. Fungal Divers. 25: 95-106.

Introduction

xxiv

Singhuber I, Zhu M, Painz S, Kopp B (2009): Aconitum in Traditional Chinese Medicine: a valuable drug or an unpredictable risk? J. Ethnopharmacol. 126: 18-30.

Stierle A, Strobel G, Stierle D (1993): Taxol and taxane production by Taxomyces andreanae an endophytic fungus of Pacifi c yew, Science 5105: 214-216.

Strobel G, Daisy B (2009): Bioprospecting for microbial Endophytes and their natural products, Microbiology and Molecular Biology Reviews 5: 535-544.

Wagner H, Bladt S (2001): Plant Drug Analysis 2nd ed. Springer, Berlin, Heidelberg,New York.

Wagner H, Bauer R, Melchart D, Pei-Gen X, Staudinger A (eds) (2011): Chromatographic Fingerprint Analysis of Herbal Medicines. Thin-layer and High Performance Liquid Chromatography of Chinese Drugs Vol. I + II, Springer-Verlag, Vienna.

Zhao Z, Liang Z, Chan K, Lu G, Lee GLM, Chen H, Li L (2010): A Unique Issue in the Standardization of Chinese Materia Medica: Processing, Planta Med. 76: 1975-1986.

xxv

Guidelines for the experimental work

Source of the herbal drugsAs described above, the herbal drugs must originate from clearly identi ed botanical species. Additionally, it must be taken into consideration that differences in cultivations, climatic conditions, time of harvest, drying and storing conditions can cause slight chromatographic deviations which cannot be avoided and are normal. Therefore it is worthwhile to investigate as many herbal drug samples of one species as possible from different geographic and ecological areas.

Extraction conditionsThe chosen extraction procedures should be rapid, but ef cient according to present scienti c knowledge and should include of the total entity of the low molecular constituents of a herbal drug. This can be achieved in most cases using alcohol (MeOH or EtOH). Additional ngerprints can be obtained by extraction using petroleum ether/hexane or chloroform (for lipophilic compounds) or water/water-acetone mixtures (for tannins, high polymeric procyanidines, and amino acids) as solvents. Polysaccharides and proteins can be characterized using their sugar- or amino acid- ngerprints after enrichment and acidic or enzymatic hydrolysis.

Chromatographic conditionsPlates/columns:

For the chromatography • TLC- or HPTLC-standardized Silica Gel F 254 (Merck) plates, in some speci c cases also aluminum oxide- or cellulose coated plates (Merck) are used. HPTLC-plates are precoated with Silica Gel of an average particle size and a narrow size distribution of 5 m as opposed to TLC material of 15 m average particle size and a broader size distribution.

For all • HPLC-analyses reversed phase C-18 or C-8 columns (LiChroCART® 125-4/250-4 LiChrospher® 100 RP-18 (5 m), Merck or LiChroCART® 125-4/250-4 LiChrospher® 60 RP select B (5 m), Merck), can be used with a Merck HITACHI L-4500 A Diode Array Detector.

A • GC-analysis is shown e.g. for Monograph No. 65 Rhizoma Acori. Apparatus: Varian GC 3800, Varian Saturn 2200 (El/Cl, msn) ion trap-mass spectrometer, Autosampler: CTC CombiPal, Separation column: Varian VF-5ms with 10 m precolumn (deactivated methyl-polysiloxan), Carrier gas: Helium.

Detection/Solvent system:

The Appendix lists the reagents and basic solvent systems used most frequently in TLC and HPLC for the detection of main structure types of drug constituents in herbal drugs.

Reference compounds:

The availability of reference compounds for the identi cation of characteristic constituents of any plant facilitates the identity (quality) proof of a herbal drug and their compounds are requirements for quantitative determination. If they cannot be isolated in the researcher’s own laboratory, some

Guidelines for the experimental work

xxvi

can be purchased from special rms. In Germany the rm Phytolab in Vestenbergsgreuth (www.phytolab.com) offers many reference compounds which are listed as “marker compounds” in the Chinese Pharmacopoeia.

Reproducibility of the ngerprint analysis

If the same technical conditions described are used, it can be expected that even with the use of instruments from other rms, very similar TLC- and HPLC- ngerprints can be obtained. If, however, for any reason, the grade of separation and/or the Rf- and Rt-values deviate from those stipulated in the Monographs, the sequence and the overall TLC-zone- and HPLC-peak pro les must still be in agreement with those documented in our Monographs.

Photography

The TL-chromatograms were developed by a Canon PowerShot G2 digital camera in a CAMAG Reprostar 3 cabinet using WinCats software (www.camag.com).

Hildebert Wagner · Rudolf Bauer · Dieter MelchartPei-Gen Xiao · Anton StaudingerEditors

Chromatographic FingerprintAnalysis of Herbal Medicines

Thin-layer and High Performance Liquid Chromatography of Chinese Drugs

Second, Revised and Enlarged Edition

Vol. 2

Photocredits:© Cover illustration and all fi gures with courtesy of the editors and authors

Coverdesign: WMXDesign GmbH, Heidelberg, GermanyTypesetting: Thomson Press (India) Ltd., Chennai, India

Printed on acid-free and chlorine-free bleached paperSPIN: 80025669

With 376 (partly coloured) fi gures

Library of Congress Control Number. 2011926593

ISBN 978-3-7091-0762-1 SpringerWienNewYork

Editors

Prof.em.Dr.Dr.h.c.mult. Hildebert WagnerLudwig-Maximilians-UniversityCenter of Pharma ResearchDepartment PharmacyGermany, Munich

Prof. Dr. Rudolf BauerKarl-Franzens-University GrazInstitute of Pharmaceutical ScienceDepartment of PharmacognosyAustria, Graz

Univ.-Prof. Dr. med. Dieter MelchartCompentence Centre for Complementary Medicine and NaturopathyTechnical University MunichGermany, Munich

Prof. Pei-Gen XiaoThe Editorial Offi ce of Chinese Herbal Medicine, BeijingInstitute of Medicinal Plant DevelopmentChinese Academy of Medical SciencesBeijing, China

Dipl.Kfm. Anton StaudingerVisiting Professor at Beijing University of Chinese MedicineExecutive Council Member of WFCMSTCM hospital Bad Kötzting, First German hospital of Traditional Chinese MedicineHospital for Psychosomatically and PsychotherapeuticallyGeneral Manager Bad Kötzting, Germany

Printed with fi nancial support of TCM-Klinik Bad Kötzting, Germany

“Chinese Drug Monographs and Analysis” originally published by Verlag für Ganzheitliche Medizin, Dr. Erich Wühr GmbH, © 2004

This work is subject to copyright.All rights are reserved, whether the whole or part of the material is concerned, specifi cally those of translation, reprinting, re-use of illustra-tions, broadcasting, reproduction by photocopying machines or similar means, and storage in data banks.

Product Liability: The publisher can give no guarantee for all the information contained in this book. This does also refer to information about drug dosage and application thereof. In every individual case the respective user must check its accuracy by consulting other phar-maceutical literature.

The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specifi c statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

© 2011 Springer-Verlag/Wien

SpringerWienNewYork is part of Springer Science+Business Mediaspringer.at

v

Contents Vol. II

Table of Contents Vol. II

Vol. I: Monographs No. 1 – 40Vol. II: Monographs No. 41 – 80

TCM-Analytical Monographs Vol. II

41 Alismatis, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46742 Carthami, Flos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47543 Epimedii, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48544 Cnidii, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49945 Lycii radicis, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50946 Lycii, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52147 Mori radicis, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53548 Mori, Folium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54949 Cimicifugae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55950 Phellodendri amurensis, Cortex Phellodendri chinensis, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57351 Lonicerae, Flos Lonicerae japonicae, Flos Lonicerae japonicae, Caulis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58752 Curcumae, Radix Curcumae longae, Rhizoma Curcumae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601 53 Dioscoreae oppositae, Rhizoma Dioscoreae hypoglaucae, Rhizoma Dioscoreae nipponicae, Rhizoma Dioscoreae septemlobae, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61554 Ganoderma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63355 Citri reticulatea, Pericarpium Citri reticulatea viride, Pericarpium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647 56 Corydalis, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66557 Dipsaci, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67758 Atractylodis lanceae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69159 Leonuri, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70760 Magnoliae, Flos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71961 Piperis longi, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72962 Sophorae fl avescentis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74363 Scutellariae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75564 Chaenomelis, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76765 Acori calami, Rhizoma Acori tatarinowii, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77766 Isatidis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79167 Tribuli, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805

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68 Ophiopogonis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81969 Eucommiae, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83170 Notoginseng, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84371 Rhei, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85772 Ginseng, Radix et Rhizoma Panacis Quinquefolii, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87573 Siegesbeckiae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89374 Salviae miltiorrhizae, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90375 Poria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92376 Cassiae, Semen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93577 Camelliae, Folium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95178 Artemisiae Scopariae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96779 Aconiti lateralis praeparata, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977 Aconiti kusnezoffi i praeparata, Radix 80 Cinnamomi, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991

Appendix:Basic Solvent Systems, reagents and columns for the TLC-, GC- and HPLC-fi ngerprint Analysis of main structure types of natural products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1009Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015Drug monograph, Marker compounds, Chemical classifi cation, Processing . . . . . . . . . . . . . 1019

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Contents alphabetically

lat. name chapter volume pageAcanthopanacis senticosus 38 I 415Aconitum kusnezo i 79 II 977Aconitum lateralis 79 II 977Acorus calamus 65 II 777Acorus tatarinowii 65 II 777Alisma orientalis 41 II 467Amomum compactum 31 I 335Amomum kravanh 31 I 335Amomum longiligulare 31 I 335Amomum villosum 31 I 335Amomum xanthioides 31 I 335Andrographis paniculata 25 I 273Anemarrhenae asphodeloides 37 I 403Angelica biserrata 9 I 99Angelica dahurica 15 I 171Angelica formosana 15 I 171Angelica pubescens 9 I 99Angelica sinensis 14 I 161Artemisia capillaris 78 II 967Artemisia scoparia 78 II 967Asarum heterotroppoides 5 I 45Asarum mandshuricum 5 I 45Asarum seoulense 5 I 45Asarum sieboldii 5 I 45Astragalus chrysopterus 8 I 83Astragalus oridus 8 I 83Astragalus membranaceus 8 I 83Astragalus mongholicus 8 I 83Astragalus tongolensis 8 I 83Atractylodes chinensis 58 II 691Atractylodes lanceae 58 II 691Atractylodes macrocephala 10 I 113Belamcanda sinensis 11 I 127Bupleurum chinense 1 I 1Bupleurum scorzonerifolium 1 I 1Camellia sinensis 77 II 951Carthamus tinctorius 42 II 475Cassia obtusifolia 76 II 935Cassia tora 76 II 935

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Chaenomeles speciosa 64 II 767Cimicifuga dahurica 49 II 559Cimicifuga heracleifolia 49 II 559Cimicifuga racemosa 49 II 559Cimicufuga foetida 49 II 559Cinnamomum cassia 80 II 991Cinnamomum ceylanicum 80 II 991Citrus reticulata 55 II 647Citrus reticulata viride 55 II 647Clematidis chinensis 33 I 355Clematidis hexapetala 33 I 355Clematidis manschurica 33 I 355Cnidium monnieri 44 II 499Codonopsis modesta 21 I 233Codonopsis pilosula 21 I 233Codonopsis tangshen 21 I 233Coptis chinensis 28 I 301Coptis deltoides 28 I 301Coptis teeta 28 I 301Corydalis yanhusuo 56 II 665Curcuma kwangsiensis 52 II 601Curcuma longa 52 II 601Curcuma phaeocaulis 52 II 601Curcuma wenyujin 52 II 601Curcuma xanthorrhiza 52 II 601Dioscorea futschauensis 53 II 615Dioscorea hypoglauca 53 II 615Dioscorea nipponica 53 II 615Dioscorea opposita 53 II 615Dioscorea septemloba 53 II 615Dipsacus asperoides 57 II 677Drynaria fortunei 19 I 211Eclipta prostrata 24 I 263Epimedium acuminatum 43 II 485Epimedium brevicornum 43 II 485Epimedium koreanum 43 II 485Epimedium pubescens 43 II 485Epimedium sagittatum 43 II 485Epimedium wushanense 43 II 485Eucommia ulmoides 69 II 831Evodia bodineiri 36 I 391Evodia of cinalis 36 I 391Evodia rutaecarpa 36 I 391

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Forsythia suspensa 35 I 381Frittilaria cirrhosa 2 I 13Frittilaria delavayi 2 I 13Frittilaria hupehensis 2 I 13Frittilaria pallidi ora 2 I 13Frittilaria przewalskii 2 I 13Frittilaria thunbergii 2 I 13Frittilaria unibraceteata 2 I 13Frittilaria ussuriensis 2 I 13Frittilaria verticillata 2 I 13Frittilaria walujewii 2 I 13Ganoderma lucidum 54 II 633Ganoderma sinensis 54 II 633Gardenia jasminoides 22 I 245Gastrodia elata 23 I 255Houttuynia cordata 6 I 59Isatis indigotica 66 II 791Leonurus japonicus 59 II 707Ligusticum chuanxiong 16 I 181Lonicera confusa 51 II 587Lonicera hypoglauca 51 II 587Lonicera japonica 51 II 587Lonicera marcanthoides 51 II 587Lycium barbarum 45/46 II 509/521Lycium chinense 45/46 II 509/521Lycopus lucidus 12 I 141Magnolia biloba 18 I 203Magnolia biondii 60 II 719Magnolia denudata 60 II 719Magnolia lilii ora 60 II 719Magnolia of cinalis 18 I 203Magnolia sprengeri 60 II 719Morus alba 47/48 II 535/549Notopterygium forbesii 13 I 151Notopterygium incisum 13 I 151Ophiopogon japonicus 68 II 819Paeonia lacti ora 26 I 281Paeonia veitchii 26 I 281Panax ginseng 72 II 875Panax notoginseng 70 II 843Panax quinquefolium 72 II 875Phellodendron amurense 50 II 573Phellodendron chinensis 50 II 573

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Pinellia ternata 7 I 71Piper longum 61 II 729Polygonum multi orum 40 I 457Poria cocos 75 II 923Pueraria lobata 20 I 221Rehmannia glutinosa 3 I 23Rehmannia hueichingensis 3 I 23Rehmannia lutea 3 I 23Rehmannia purpurea 3 I 23Rheum of cinale 71 II 857Rheum palmatum 71 II 857Rheum tanguticum 71 II 857Salvia miltiorrhiza 74 II 903Schisandra chinensis 4 I 37Scrophularia ningpoensis 39 I 427Scutellaria baicalensis 63 II 455Siegesbeckia glabrescens 73 II 893Siegesbeckia orientalis 73 II 893Siegesbeckia pubescens 73 II 893Sinomenium acutum 34 I 369Sinomenium cinerum 34 I 369Sophora avescens 27 I 291Sophora japonica 27 I 291Stephania tetrandra 29 I 311Tribulus terrestris 67 II 805Uncaria hirsuta 32 I 343Uncaria macrophylla 32 I 343Uncaria rhynchophylla 32 I 343Uncaria sessilifructus 32 I 343Uncaria sinensis 32 I 343Uncaria tomentosa 32 I 343Zanthoxylum armatum 17 I 191Zanthoxylum bungeanum 17 I 191Zanthoxylum piperitum 17 I 191Zanthoxylum schinifolium 17 I 191Ziziphus jujuba 30 I 325

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chin. name Chapter volume pageBaishao 26 I 281Baizhi 15 I 171Baizhu 10 I 113Banlangen 66 II 791Banxia 7 I 71Beimu 2 I 13Bibo 61 II 729Cangzhu 58 II 691Chaihu 1 I 1Cha-yeh 77 II 951Chenpi 55 II 647Chishao 26 I 281Chuanshanlong 53 II 615Chuanxinlian 25 I 273Chuanxiong 16 I 181Ciwujia 38 I 181Dahuang 71 II 857Danggui 14 I 161Dangshen 21 I 233Danshen 74 II 903Digupi 45 II 509Dihuang 3 I 23Duhuo 9 I 99Duzhong 69 II 831Ezhu 52 II 601Fangji 29 I 311Fenbixie 53 II 615Fuling 75 II 923Fuzi 79 II 977Gegen 20 I 221Gouqizi 46 II 521Gouteng 32 I 343Guanhuangbo 50 II 573Gusuibu 19 I 211Heshouwu 40 I 439Honghuo 42 II 475Houpo 18 I 203Huaihua 27 I 291Huaimi 27 I 291Huajiao 17 I 191

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Huangbo 50 II 573Huanglian 28 I 301Huangqi 8 I 83Huangqin 63 II 755Jianghuang 52 II 601Jili 67 II 805Jinyinhua 51 II 587Juemingzi 76 II 935Kushen 62 II 743Lianqiao 35 I 381Lingzhi 54 II 633Maidong 68 II 819Mianbixie 53 II 615Mohanlian 24 I 263Mugua 64 II 767Qianghuo 13 I 151Qingfengteng 34 I 369Qingpi 55 II 647Rendongteng 51 II 587Renshen 72 II 875Rougui 80 II 991Sangbaipi 47 II 535Sangye 48 II 549Sanqi 70 II 843Shanyao 53 II 615Shanyinhua 51 II 587Sharen 31 I 335Shechuangzi 44 II 499Shegan 11 I 127Shengma 49 II 559Shichangpu 65 II 777Suanzaoren 30 I 325Tianma 23 I 255Weilingxian 33 I 355Wuweizi 4 I 37Wuzhuyu 36 I 391Xinyi 60 II 719Xixiancao 73 II 893Xixin 5 I 45Xiyangshen 72 II 875Xuaanshen 39 I 427

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Xuduan 57 II 677Yanhusuo 56 II 665Yimucae 59 II 707Yinchen 78 II 967Yinyanghuo 43 II 485Yujin 52 II 601Yuxingxao 6 I 59Zelan 12 I 141Zexie 41 II 467Zhangchangpu 65 II 777Zhicaowu 79 II 977Zhimu 37 I 403Zhizi 22 I 245