Chromatographic Fingerprint Analysis of Herbal Medicines

Hildebert Wagner • Rudolf Bauer • Dieter Melchart Anton Staudinger Editors

Chromatographic Fingerprint Analysis of Herbal Medicines

Thin-Layer and High Performance Liquid Chromatography of Chinese Drugs

Vol. 4

Editors Hildebert Wagner Center of Pharma Research Ludwig-Maximillians-University Munich Germany

Rudolf Bauer Institute of Pharmaceutical ScienceUniversity of Graz Graz Austria

Dieter Melchart Klinikum rechts der Isar Kompetenzzentrum Komplementärmedizin Munich Germany

Anton Staudinger TCM-Klinik Bad Kötzting Bad Kötzting Germany

ISBN 978-3-319-32326-8 ISBN 978-3-319-32328-2 (eBook) DOI 10.1007/978-3-319-32328-2

Library of Congress Control Number: 2014945949

© Springer International Publishing Switzerland 2016 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifi cally the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfi lms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, 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. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made.

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This Springer imprint is published by Springer Nature The registered company is Springer International Publishing AG Switzerland

v

Contents

Vol. I: Monographs No. 1 – 40Vol. II: Monographs No. 41 – 80Vol. III: Monographs No. 81 – 103

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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28127. Sophorae, Flos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29128. Coptidis, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301

vi

29. 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 ngerprintAnalysis of main structure types of natural products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457Drug monograph, Marker compounds, Chemical classifi cation, Processing . . . . . . . . . . . . . . . . . . . . . . . . 461

Contents Vol. I

vii

Table of Contents Vol. II

Vol. I: Monographs No. 1 – 40Vol. II: Monographs No. 41 – 80Vol. III: Monographs No. 81 – 103

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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587

52. Curcumae, Radix Curcumae longae, Rhizoma Curcumae, Rhizoma. . . . . . . . . . . . . . . . . . . . . . . . . . . 60153. Dioscoreae oppositae, Rhizoma

Dioscoreae hypoglaucae, Rhizoma Dioscoreae nipponicae, Rhizoma Dioscoreae septemlobae, Rhizoma. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615

54. Ganoderma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63355. Citri reticulatea, Pericarpium Citri reticulatea viride, Pericarpium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64756. 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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80568. Ophiopogonis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81969. Eucommiae, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83170. Notoginseng, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84371. Rhei, Radix et Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85772. Ginseng, Radix et Rhizoma

Panacis Quinquefolii, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 875

Contents Vol. II

viii

73. 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, Radix80. Cinnamomi, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991

Appendix:

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

Contents Vol. II

ix

Table of Contents Vol. III

Vol. I: Monographs No. 1 – 40Vol. II: Monographs No. 41 – 80Vol. III: Monographs No. 81 – 103

TCM-Analytical Monographs Vol. III

81. Crataegi, Folium/Fructus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182. Cyperi, Rhizoma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1783. Lycopodii, Herba. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2784. Saposhnikoviae, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3585. Glycyrrhizae, Radix et Rhizoma. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4386. Gynostemmatis, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5587. Sarcandrae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6988. Ligustri lucidi, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7989. Moutan, Cortex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9190. Peucedani, Radix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10591. Achyranthis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11992. Bambusae in Taenia, Caulis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13193. Lysimachiae christiniae, Herba. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14594. Desmodii styracifolii, Herba. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15995. Retinervus Luffae, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17196. Oldenlandiae, Herba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18597. Siraitiae/Momordicae, Fructus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19798. Morindae offi cinalis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20599. Apocyni veneti, Folium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217100. Eriocauli, Flos . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229101. Spatholobi, Caulis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235102. Aucklandiae, Radix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243103. Platycodonis, Radix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267

Contents Vol. III

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Table of Contents Vol. IV

Vol. I: Monographs No. 1 – 40Vol. II: Monographs No. 41 – 80Vol. III: Monographs No. 81 – 103

TCM-Analytical Monographs Vol. IV

104. Cortex, Albiziae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105. Cortex, Fraxini . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11106. Fructus, Arctii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19107. Fructus, Corni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27108. Fructus, Kochiae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37109. Fructus, Psoraleae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47110. Fructus/Semen, Trichosanthis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59111. Fructus, Viticis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71112. Fructus, Xanthii. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79113. Herba Artemisiae annuae/Folium Artemisiae argyi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91114. Herba, Ephedrae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107115. Herba, Violae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115116. Lignum, Sappan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125117. Radix, Gentianae macrophyllae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137118. Radix, Trichosanthis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147119. Ramulus, Mori . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157120. Semen, Celosiae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169121. Semen Nigrum, Sesami . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181122. Semen, Sinapis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191123. Semen, Vaccariae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203124. Semen/Herba, Plantaginis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213125. Spica, Prunellae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239

Contents Vol. IV

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Lat. name Chapter Page Albizia julibrissin 104 1 Arctium lappa 106 19 Artemisia annua 113 91 Artemisia argyi 113 91 Caesalpinia sappan 116 125 Celosia argentea 120 169 Cornus offi cinalis 107 27 Ephedra sinica 114 107 Fraxinus chinensis 105 11 Fraxinus excelsior 105 11 Fraxinus rhynchophylla 105 11 Fraxinus szaboana 105 11 Gentiana macrophylla 117 137 Kochia scoparia 108 37 Morus alba 119 157 Plantago asiatica 124 213 Plantago depressa 124 213 Prunella vulgaris 125 225 Psoralea corylifolia 109 47 Sesamum indicum 121 181 Sinapis alba 122 191 Trichosanthes kirilowii 110/118 59/147 Trichosanthes rosthornii 110/118 59/147 Vaccaria segetalis 123 203 Viola tricolor 115 115 Viola yedoensis 115 115 Vitex agnus-castus 111 71 Vitex trifolia 111 71 Xanthium sibiricum 112 79

Contents Alp habetically

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Authors’ Contributions

• Supervisor and responsible for the correct performance of the Analytical Monographs of Chinese Herbal Drugs Prof. Dr. Dr. h.c. Hildebert Wagner, Special Analytical Laboratory of the Department of Pharmacy of the University of Munich, Butenandtstr. 5, 81377 Munich; e-mail. h.wagner@cup.uni-muenchen.de

Acknowledgements

• The editors wish to express their deep gratitude to the TCM Clinic Bad Kötzting Mr. A. Staudinger for fi nancial support and Prof. A. Vollmar, LMU Munich, Department of Pharmacy, for the supply of labora-tory space and various facilities for the chemical and technical investigations of the TCM drugs.

• We are deeply indebted to our technical assistants Mrs. Stefanie Püls and Mrs. Talee Barghouti.

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Introd uction

• Legislation Among the various prerequisites for a perfect quality proof of these herbal drugs, authentication and safety proof take fi rst precedence. Identifi cation was in former times primarily synonymous with the macroscopic and microscopic botanical authenticity. Since that time, however, chemical composition and particularly the complex entities of the low molecular constituents have become of greater interest for oral medicinal application and thus in evaluating the pharmacological effects and therapeutic effi cacy of the plant drug extracts obtained by decoction or other extraction processes.

• Independent of the specifi c national drug regulations for countries around the world, there is also an inter-national consensus that all TCM drugs must meet certain, stipulated high-quality standards. Additionally, it must be guaranteed that all TCM drugs prescribed by physicians are safe for patients. The safety proof aims mainly to exclude any kind of possible falsifi cations of the herbal drugs and the limitation of concen-trations of heavy metals, afl atoxins and defi ned microbial adulterations.

• Applied Methods of the Qualifi ed Proof The main method used is TLC (thin layer chromatography), which allows us to present the visualized main characteristic constituents in the form of coloured TLC photographs. The second method, used globally, is HPLC (high pressure liquid chromatography) in the form of a so-called fi ngerprint analysis. This tech-nique allows us to detect the complex entities of all low molecular constituents of a plant drug extract, with the advantage that the single constituents can be made visible in the form of peak profi les. Additionally, the single constituents can be quantifi ed by using online recordable UV spectra with the diode array tech-nique. It is also possible to gain preliminary information as to which chemical structure type the single compounds may belong. From this year forward, LC-MS (liquid chromatography-mass spectroscopy) is also available for the analysis of plant extracts whose chemical compositions have previously been only minimally investigated.

• Publication of the Analytical Monographs of Investigated Herbal Chinese Drugs The following volumes were published by Springer, Vienna and New York, with fi nancial support from the TCM Clinic Bad Kötzting; Wagner, H., Bauer, R., Melchart, D., Xiao, P.-G., Staudinger, A. (Eds.)

– Vols. I and II (2011) containing 80 analytical monographs – Vol. III (2015) containing 23 analytical monographs – Vol. IV (2016) containing 22 analytical monographs – Vol. V (in preparation; publication scheduled for February/March 2017)

• Note: All single analytical monographs that are already edited can be downloaded at http://www.springer.com/de/book/9783709107621

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Prospects for the Improvement of the Quality Proof of Chinese Herbal Drugs

1. Authenticity of TCM drugs not defi nitely assessable Some herbal drugs are not yet produced under controlled cultivation but originate from wild collections. Even if they 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 a variety of conditions. Therefore, their chemical authen-ticity and homogeneity within a defi ned plant species often cannot be guaranteed. We have thus investigated as many herbal drug samples as we were able to acquire from different districts, climate zones and markets in China, as well as reference drugs from some German herbal drug fi rms that also import herbal drugs from China.

2. For 5–10 % of imported plant drugs from China, we do not receive specifi c information about the plant part (Flos, Fructus, Semen, Folium, Cortex or Radix and Rhizoma) from which they were collected. Such drugs are specifi ed as “herba” analogues. For these drug samples, it cannot be expected that the TLC and HPLC chemi-cal fi ngerprints are very homogenous. Not all parts of a herbal drug contain the same chemical constituents. The documentation in the corresponding herbal analytical monographs confi rms this judgement (see e.g. Herba Leonuri, Vol. II; Herba Lysimachiae, Vol. III; or Herba Violae, Vol. IV). Therefore, it will be necessary that this discrepancy has to be corrected in the future. Otherwise, it cannot be expected that the results of clini-cal application can be reproduced.

3. Uncertain botanical nomenclature The non-uniform nomenclature for the same plant in various regions of China can cause impermissible substi-tutions or falsifi cations. This occurred some years ago when the root of Stephania tetrandra (Hanfangji) was mistaken for the root of Aristolochia fangji (Guanfangji). The latter of both contains the carcinogenic aristolochic acid which can produce severe nephrotoxic side effects. A similar Chinese drug is the tetraploid Acorus tatarinowii which differs in a very high content of carcinogenic β-asarone from that of the diploid Acorus calamus , known offi cially in most western countries. Meanwhile special chromatographic methods were developed and described in the analytical monographs to avoid such falsifi cations.

4. Great variability of plant species Several herbal drug monographs of the Chinese Pharmacopoeia list more than two species or subspecies and sometimes up to eight species labelled as synonyms, subspecies or subvarieties. It is assumed that all species contain the same constituents in the same amount. In our 20 years running TLC- and HPLC-fi ngerprint inves-tigations, we have shown that in many cases considerable differences were detectable between the single spe-cies and the main offi cial drugs. Correspondingly, it may be suggested that a great number of the “subspecies” do not possess the same pharmacological and therapeutic effi cacy. This fact must be recognized and taken into consideration!

Introduction

xix

Guidelines for the Experimental Work

Source of the Herbal Drugs

As discussed in the preceding paragraph, the herbal drugs must originate from clearly identifi ed botanical spe-cies. 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 can be obtained from different geographic and ecological areas.

Extraction Conditions

The chosen extraction procedures should be fast but effi cient according to present scientifi c knowledge and inclu-sive 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 fi ngerprints can be obtained by extraction using petroleum ether/hexane or chloroform (for lipophilic compounds) or water/water-acetone mixtures (for tannins, high polymeric procyani-dins and amino acids) as solvents. Polysaccharides and proteins can be characterized via their sugar or amino acid fi ngerprints after enrichment and acidic or enzymatic hydrolysis.

Chromatographic Conditions

Plates/Columns • For the chromatography TLC- or HPTLC-standardized Silica Gel F254 (Merck) plates, in some specifi c

cases also aluminium 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 μm (as opposed to TLC material of 15 μm average particle size and a broader size distribution).

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

Detection/Solvent System In the appendix of Volumes 1 and 2 (p. 451/1009), the most used reagents and basic solvent systems in TLC and HPLC are listed for the detection of main structure types of drug constituents in herbal drugs.

Reference Compounds The availability of reference compounds which are characteristic of any herbal drug and at the same time repre-sent the main pharmacologically active constituents of any plant facilitates the identity (quality) proof of a herbal drug and is a requirement for quantitation determination. If they cannot be isolated in the researcher’s own labora-tory, some of them can also be purchased from special fi rms. In Germany the fi rm PhytoLab in Vestenbergsgreuth ( www.phytolab.com ) offers many reference compounds which are listed as “marker compounds” in the Chinese Pharmacopoeia.

xx

Reproducibility of the Fingerprint Analysis If the same technical conditions described are used, it can be expected that even with the use of instruments from other fi rms, nearly identical TLC and HPLC fi ngerprints must be obtained. If, however, for any reason, the grade of separation and/or the R f and Rt values deviate from those stipulated in the monographs, the sequence and the overall TLC zone and HPLC peak profi les must in any case be identical.

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

Guidelines for the Experimental Work