m ethods in m olecular b iology
TRANSCRIPT
M E T H O D S I N M O L E C U L A R B I O L O G Y ™
Series EditorJohn M. Walker
School of Life SciencesUniversity of Hertfordshire
Hat fi eld, Hertfordshire, AL10 9AB, UK
For further volumes:http://www.springer.com/series/7651
Chiral Separations
Methods and Protocols
Second Edition
Edited by
Gerhard K.E. Scriba
Department of Pharmaceutical Chemistry, Friedrich Schiller University Jena, Jena, Germany
EditorGerhard K.E. ScribaDepartment of Pharmaceutical ChemistryFriedrich Schiller University JenaJena, Germany
ISSN 1064-3745 ISSN 1940-6029 (electronic)ISBN 978-1-62703-262-9 ISBN 978-1-62703-263-6 (eBook)DOI 10.1007/978-1-62703-263-6Springer New York Heidelberg Dordrecht London
Library of Congress Control Number: 2012952732
© Springer Science+Business Media, LLC 2013This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, speci fi cally the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on micro fi 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. Exempted from this legal reservation are brief excerpts in connection with reviews or scholarly analysis or material supplied speci fi cally for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. Duplication of this publication or parts thereof is permitted only under the provisions of the Copyright Law of the Publisher’s location, in its current version, and permission for use must always be obtained from Springer. Permissions for use may be obtained through RightsLink at the Copyright Clearance Center. Violations are liable to prosecution under the respective Copyright Law.The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a speci fi c statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.While the advice and information in this book are believed to be true and accurate at the date of publication, neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or omissions that may be made. The publisher makes no warranty, express or implied, with respect to the material contained herein.
Printed on acid-free paper
Humana Press is a brand of SpringerSpringer is part of Springer Science+Business Media (www.springer.com)
Dedication
To Beate, Sabrina, and Rebecca
vii
What can more resemble my hand or my ear, and be more equal in all points, than its image in a mirror? And yet, I cannot put such a hand as is seen in the mirror in the place of its original.
Immanuel Kant Prolegomena to Any Future Metaphysics That Will Be Able to Come Forward as Science (1783)
ix
Preface
The importance of the stereochemistry of compounds is well recognized in chemistry and life sciences since Louis Pasteur discovered the phenomenon of chirality in 1848. The enantiomers of chiral compounds often differ in their biological, pharmacological, toxico-logical, and/or pharmacokinetic pro fi le. This has become evident speci fi cally in pharma-ceutical sciences, but it also affects chemistry, biology, food chemistry, forensics, etc., and is re fl ected in the requirements for chiral compounds by regulatory authorities worldwide. For example, the Food and Drug Administration (FDA) and the European Medicines Agency (EMA) require the development of a single enantiomer of a drug candidate if the enantiomers differ in their pharmacological action, toxicological pro fi le, etc. As a conse-quence, seven drugs of the top ten drugs (not counting biotechnological drugs) according to their sales in the USA in 2010 ( www.drugs.com/top200.html , accessed February 21, 2012) are single enantiomer drugs, while two drugs are achiral compounds. One product is a combination of a chiral and a racemic drug. In fact, the top three products are single enantiomer drugs. However, the importance of chirality does not stop here but is impor-tant to any research in life sciences.
Generally, there is a great demand for analytical methods that are able to discriminate between enantiomers in order to analyze the enantiomeric purity of compounds from natu-ral or chemical sources not only in pharmaceutical sciences but in any fi eld of bioactive compounds including chemistry, biology, biochemistry, forensic and environmental sci-ences, and many others. Chromatographic techniques dominated the fi eld of enantiosepa-rations early on, but electrophoretic methods have gained increasing importance in recent years. While some compounds may be analyzed only with one technique based on their physicochemical properties, often the analyst can chose between two or more analytical techniques for a given analyte. This requires knowledge of the strengths and weaknesses of each technique in order to select the most appropriate method for the given problem.
The focus of Chiral Separations: Methods and Protocols, 2nd edition is clearly on analyti-cal separation sciences by chromatographic and electrophoretic techniques although simu-lated moving bed chromatography has also been included, which is primarily used as a preparative method. The book does not claim to comprehensively cover each possible chiral separation mechanism but to give an overview and especially practically oriented applica-tions of the most important analytical techniques in chiral separation sciences. Thus, the book follows the well-established scheme of the Methods and Protocols series. Some review chapters give an overview of the current state of art in the respective fi eld. However, most chapters are devoted to the description of the typical analytical procedures providing reli-able and established procedures for the user. Critical points are highlighted so that the user is enabled to transfer the described method to his/her actual separation problem.
Sixty-four authors from 34 research laboratories in 17 countries have contributed by sharing their insight and expert knowledge of the techniques. I would like to take the opportunity to thank all authors for their efforts and valuable contributions.
x Preface
Chiral Separations: Methods and Protocols, 2nd edition should be helpful for analytical chemists working on stereochemical problems in fi elds of pharmacy, chemistry, biochemis-try, food chemistry, molecular biology, forensics, environmental sciences, or cosmetics in academia, government, or industry.
Jena, Germany Gerhard K.E. Scriba
xi
Contents
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ixContributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv
1 Chiral Recognition in Separation Science: An Overview. . . . . . . . . . . . . . . . . . 1Gerhard K.E. Scriba
2 Enantioseparations by Thin-Layer Chromatography . . . . . . . . . . . . . . . . . . . . 29Massimo Del Bubba, Leonardo Checchini, Alessandra Cincinelli, and Luciano Lepri
3 Gas-Chromatographic Enantioseparation of Unfunctionalized Chiral Hydrocarbons: An Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45Volker Schurig and Diana Kreidler
4 HPLC Enantioseparation on Cyclodextrin-Based Chiral Stationary Phases. . . . 69Yong Wang and Siu Choon Ng
5 Enantioseparations by High-Performance Liquid Chromatography Using Polysaccharide-Based Chiral Stationary Phases: An Overview. . . . . . . . . 81Bezhan Chankvetadze
6 Common Screening Approaches for Efficient Analytical Method Development in LC and SFC on Columns Packed with Immobilized Polysaccharide-Derived Chiral Stationary Phases . . . . . . . . . . . . . . . . . . . . . . . 113Pilar Franco and Tong Zhang
7 Chiral Separations by HPLC on Immobilized Polysaccharide Chiral Stationary Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127Imran Ali, Zeid A. AL-Othman, and Hassan Y. Aboul-Enein
8 Enantioseparations by High-Performance Liquid Chromatography Using Macrocyclic Glycopeptide-Based Chiral Stationary Phases: An Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137István Ilisz, Anita Aranyi, Zoltán Pataj, and Antal Péter
9 Enantioseparations of Primary Amino Compounds by High-Performance Liquid Chromatography Using Chiral Crown Ether-Based Chiral Stationary Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165Myung Ho Hyun
10 Screening of Pirkle-Type Chiral Stationary Phases for HPLC Enantioseparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177Gregory K. Webster and Ted J. Szczerba
11 Enantioseparations by High-Performance Liquid Chromatography Based on Chiral Ligand-Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191Benedetto Natalini, Roccaldo Sardella, and Federica Ianni
xii Contents
12 Enantioseparations by High-Performance Liquid Chromatography Using Molecularly Imprinted Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209David A. Spivak
13 Chiral Mobile Phase Additives in HPLC Enantioseparations . . . . . . . . . . . . . . 221Lushan Yu, Shengjia Wang, and Su Zeng
14 Chiral Benzofurazan-Derived Derivatization Reagents for Indirect Enantioseparations by HPLC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233Toshimasa Toyo’oka
15 Separation of Racemic 1-(9-Anthryl)-2,2,2-trifluoroethanol by Sub-/Supercritical Fluid Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . 249Xiqin Yang, Leo Hsu, and Gerald Terfloth
16 Chiral Separations by Simulated Moving Bed Method Using Polysaccharide-Based Chiral Stationary Phases. . . . . . . . . . . . . . . . . . . . . . . . . 257Toshiharu Minoda
17 Enantioseparations by Capillary Electrophoresis Using Cyclodextrins as Chiral Selectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271Gerhard K.E. Scriba and Pavel Jáč
18 Application of Dual Cyclodextrin Systems in Capillary Electrophoresis Enantioseparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289Anne-Catherine Servais and Marianne Fillet
19 Enantioseparations in Nonaqueous Capillary Electrophoresis Using Charged Cyclodextrins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297Anne-Catherine Servais and Marianne Fillet
20 Use of Macrocyclic Antibiotics as the Chiral Selectors in Capillary Electrophoresis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307Chengke Li and Jingwu Kang
21 Application of Polymeric Surfactants in Chiral Micellar Electrokinetic Chromatography (CMEKC) and CMEKC Coupled to Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319Jun He and Shahab A. Shamsi
22 Cyclodextrin-modified Micellar Electrokinetic Chromatography for Enantioseparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349Wan Aini Wan Ibrahim, Dadan Hermawan, and Mohd Marsin Sanagi
23 Cyclodextrin-Mediated Enantioseparation in Microemulsion Electrokinetic Chromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363Claudia Borst and Ulrike Holzgrabe
24 Chiral Separations by Capillary Electrophoresis Using Proteins as Chiral Selectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377Jun Haginaka
25 Enantioseparation by Chiral Ligand-Exchange Capillary Electrophoresis . . . . . 393Yi Chen and Lijuan Song
26 Experimental Design Methodologies in the Optimization of Chiral CE or CEC Separations: An Overview . . . . . . . . . . . . . . . . . . . . . . . 409Bieke Dejaegher, Debby Mangelings, and Yvan Vander Heyden
xiiiContents
27 Chiral Capillary Electrophoresis–Mass Spectrometry . . . . . . . . . . . . . . . . . . . . 429Elena Domínguez-Vega, Antonio L. Crego, and Maria Luisa Marina
28 Application of Chiral Ligand-Exchange Stationary Phases in Capillary Electrochromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443Martin G. Schmid
29 Polysaccharide-Derived Chiral Stationary Phases in Capillary Electrochromatography Enantioseparations. . . . . . . . . . . . . . . . . . . . . . . . . . . 457Zhenbin Zhang, Hanfa Zou, and Junjie Ou
30 Open Tubular Molecular Imprinted Phases in Chiral Capillary Electrochromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469Won Jo Cheong and Song Hee Yang
31 Enantioseparations in Capillary Electrochromatography Using Sulfated Poly β-Cyclodextrin-Modified Silica-Based Monolith as Stationary Phase. . . . . 489Ruijuan Yuan and Guosheng Ding
32 Cyclodextrin-Mediated Enantioseparations by Capillary Electrochromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505Dorothee Wistuba and Volker Schurig
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
xv
Contributors
HASSAN Y. ABOUL-ENEIN • National Pharmaceutical and Medicinal Chemistry Department , Research Centre , Cairo , Egypt
IMRAN ALI • Department of Chemistry , Jamia Millia Islamia (Central University) , New Delhi , India
ZEID A. AL-OTHMAN • Department of Chemistry , King Saud University , Riyadh , Kingdom of Saudi Arabia
ANITA ARANYI • Department of Inorganic and Analytical Chemistry , University of Szeged , Szeged , Hungary
CLAUDIA BORST • Institute of Pharmacy and Food Chemistry, University of Würzburg , Würzburg , Germany
MASSIMO DEL BUBBA • Department of Chemistry , University of Florence , Sesto Fiorentino , Italy
BEZHAN CHANKVETADZE • Institute of Physical and Analytical Chemistry, Tbilisi State University , Tbilisi , Georgia
LEONARDO CHECCHINI • Department of Chemistry , University of Florence , Sesto Fiorentino , Italy
YI CHEN • Key Laboratory of Analytical Chemistry for Living Biosystems , Chinese Academy of Sciences , Beijing , China
WON JO CHEONG • Department of Chemistry , Inha University , Incheon , South Korea ALESSANDRA CINCINELLI • Department of Chemistry , University of Florence ,
Sesto Fiorentino , Italy ANTONIO L. CREGO • Department of Analytical Chemistry , University of Alcalá ,
Alcalá de Henares , Spain BIEKE DEJAEGHER • Department of Analytical Chemistry and Pharmaceutical Technology ,
Vrije Universiteit Brussel , Brussels , Belgium GUOSHENG DING • Analysis Center, Tianjin University , Tianjin , China ELENA DOMÍNGUEZ-VEGA • Department of Analytical Chemistry , University of Alcalá ,
Alcalá de Henares , Spain MARIANNE FILLET • Department of Pharmaceutical Sciences , University of Liège , Liège ,
Belgium PILAR FRANCO • Chiral Technologies Europe , Illkirch , France JUN HAGINAKA • School of Pharmacy and Pharmaceutical Sciences, Mukogawa Women’s
University , Nishinomiya , Japan JUN HE • Department of Chemistry , Center of Biotechnology and Drug Design,
Georgia State University , Atlanta , GA , USA DADAN HERMAWAN • Department of Chemistry , Universiti Teknologi Malaysia , Johor ,
Malaysia YVAN VANDER HEYDEN • Department of Analytical Chemistry and Pharmaceutical
Technology , Vrije Universiteit Brussel , Brussels , Belgium ULRIKE HOLZGRABE • Institute of Pharmacy and Food Chemistry, University of Würzburg ,
Würzburg , Germany
xvi Contributors
LEO HSU • GlaxoSmithKline Research and Development , King of Prussia , PA , USA MYUNG HO HYUN • Department of Chemistry and Chemistry , Pusan National University ,
Busan , South Korea FEDERICA IANNI • Dipartimento di Chimica e Tecnologia del Farmaco , Università degli
Studi di Perugia , Perugia , Italy WAN AINI WAN IBRAHIM • Separation Science and Technology Group (SepSTec) ,
Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia , Johor , Malaysia
ISTVÁN ILISZ • Department of Inorganic and Analytical Chemistry , University of Szeged , Szeged , Hungary
PAVEL JÁČ • Department of Pharmaceutical/Medicinal Chemistry , Friedrich Schiller University Jena , Jena , Germany
JINGWU KANG • Chinese Academy of Sciences, Shanghai Institute of Organic Chemistry , Shanghai , China
DIANA KREIDLER • Institute of Organic Chemistry, University of Tübingen , Tübingen , Germany
LUCIANO LEPRI • Department of Chemistry , University of Florence , Sesto Fiorentino , Italy CHENGKE LI • Chinese Academy of Sciences, Shanghai Institute of Organic Chemistry ,
Shanghai , China DEBBY MANGELINGS • Department of Analytical Chemistry and Pharmaceutical
Technology , Vrije Universiteit Brussel , Brussels , Belgium MARIA LUISA MARINA • Department of Analytical Chemistry , University of Alcalá , Alcalá
de Henares , Spain TOSHIHARU MINODA • Daicel Corporation , Niigata , Japan BENEDETTO NATALINI • Dipartimento di Chimica e Tecnologia del Farmaco , Università
degli Studi di Perugia , Perugia , Italy SIU CHOON NG • School of Chemical and Biomedical Engineering, Nanyang
Technological University , Singapore , Singapore JUNJIE OU • National Chromatographic R&A Center, Dalian Institute of Chemical
Physics , Dalian , China ZOLTÁN PATAJ • Department of Inorganic and Analytical Chemistry , University of Szeged ,
Szeged , Hungary ANTAL PÉTER • Department of Inorganic and Analytical Chemistry , University of Szeged ,
Szeged , Hungary MOHD MARSIN SANAGI • Department of Chemistry , Universiti Teknologi Malaysia , Johor ,
Malaysia ROCCALDO SARDELLA • Dipartimento di Chimica e Tecnologia del Farmaco , Università
degli Studi di Perugia , Perugia , Italy MARTIN G. SCHMID • Institute of Pharmaceutical Sciences, Karl-Franzens-University ,
Graz , Austria VOLKER SCHURIG • Institute of Organic Chemistry, University of Tübingen , Tübingen ,
Germany GERHARD K. E. SCRIBA • Department of Pharmaceutical/Medicinal Chemistry , Friedrich
Schiller University Jena , Jena , Germany ANNE-CATHERINE SERVAIS • Department of Pharmaceutical Sciences , University of Liège ,
Liège , Belgium
xviiContributors
SHAHAB A. SHAMSI • Department of Chemistry , Center of Biotechnology and Drug Design, Georgia State University , Atlanta , GA , USA
LIJUAN SONG • Chinese Academy of Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems , Beijing , China
DAVID A. SPIVAK • Department of Chemistry , Louisiana State University , Baton Rouge , LA , USA
TED J. SZCZERBA • Regis Technologies , Morton Grove , IL , USA GERALD TER FL OTH • GlaxoSmithKline Research and Development , King of Prussia ,
PA , USA TOSHIMASA TOYO’OKA • Graduate School of Pharmaceutical Sciences, University of Shizuoka ,
Shizuoka , Japan SHENGJIA WANG • Department of Pharmaceutical Analysis and Drug Metabolism ,
Zhejiang University , Hangzhou , China YONG WANG • Department of Chemistry , School of Sciences, Tianjin University ,
Tianjin , China GREGORY K. WEBSTER • Abbott Laboratories , Abbott Park , IL , USA DOROTHEE WISTUBA • Institute of Organic Chemistry, University of Tübingen ,
Tübingen , Germany SONG HEE YANG • Department of Chemistry , Inha University , Incheon , South Korea XIQIN YANG • GlaxoSmithKline Research and Development , King of Prussia , PA , USA LUSHAN YU • Department of Pharmaceutical Analysis and Drug Metabolism , Zhejiang
University , Hangzhou , China RUIJUAN YUAN • School of Chinese Pharmacy, Beijing University of Chinese Medicine ,
Beijing , China SU ZENG • Department of Pharmaceutical Analysis and Drug Metabolism , Zhejiang
University , Hangzhou , China TONG ZHANG • Chiral Technologies Europe , Illkirch , France ZHENBIN ZHANG • National Chromatographic R&A Center, Dalian Institute of Chemical
Physics , Dalian , China HANFA ZOU • National Chromatographic R&A Center, Dalian Institute of Chemical
Physics , Dalian , China