“This book represents an extensive collection of essential fundamentals of molecular imprinting and state-of-the-art technologies of its sensor applications. It describes various bio- and chemo-sensing methods using molecular imprinting and will be M of great interest to students and researchers in chemistry, physics, and materials science.” Prof. Kiyoshi Toko Kyushu University, Japan o “Sensors that memorize the shape and size of molecules can detect all targets. Such an ultimate concept of sensing has been realized by molecularly imprinted sensors. l H This handbook excellently presents the features of these sensors.” e a Prof. Katsuhiko Ariga n National Institute for Materials Science, Japan c d b o Molecular imprinting has attracted a great deal of scientific attention because of the u o enormous opportunities it opens in the fields of separation, catalysis, and analysis. Its k advantages enable to target a wide class of substances ranging from small molecules to o big conglomerates, such as proteins and even cells. In recent years, sensor applications l f based on molecular imprinting have started to attract greater attention because of the a easy creation of robust receptor sites with high specificity and sensitivity toward a target compound. This book is probably the first collection of contributions by distinguished experts that provides a comprehensive overview on the specific challenges of molecular r imprinting in sensor applications. It covers various molecular imprinting approaches, so that a perspective of future device ensembles for sensing is acquired. The text lays I particular emphasis on fundamental aspects as well as novel ideas in the context of sensor applications. It also highlights the operation principles of various sensor m transducers that are generally employed in combination with molecular imprinting edited by recognition elements. Seung-Woo Lee Seung-Woo Lee obtained his doctorate in chemistry and biochemistry p Toyoki Kunitake from Kyushu University, Japan, in 1999. After postdoctoral work at Kyushu University, he worked for Frontier Research System, RIKEN, on projects based at the Spatio-Temporal Function Materials r Research group. Dr. Lee now works for the Graduate School of i Environmental Engineering at the University of Kitakyushu, Japan. His scientific interests include metal oxide thin-film-based molecular imprinting n L e and chemical sensors. e Handbook of t Molecular Toyoki Kunitake received his doctorate in chemistry from the University of Pennsylvania, USA, in 1962. After a year’s stay at i K the California Institute of Technology as a postdoctoral fellow, he n u returned to his alma mater as associate professor and retired from n i there as professor in 1999. He was dean of engineering, leader of t g a Imprinting major national research projects, vice president of the University k of Kitakyushu, and group director of Spatio-Temporal Function Materials e Research at Frontier Research System, RIKEN. Dr. Kunitake is currently president of the Kitakyushu Foundation for the Advancement of Industry, Science and Technology. His research interests include supramolecular chemistry, particularly Advanced Sensor Applications synthetic bilayer membranes, and molecular recognition at organic and inorganic interfaces. V271 ISBN-13 978-981-4316-65-1 TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2012 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20120816 International Standard Book Number-13: 978-9-81436-432-4 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reason- able efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organiza- tion that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Part 1 Fundamentals of Molecular Imprinting and Sensor Applications 1 1. Fundamentals and Perspectives of Molecular Imprinting in Sensor Applications 3 Seung-Woo Lee, Sergiy Korposh, Roman Selyanchyn, and Toyoki Kunitake 1.1 Introduction 3 1.2 Molecular Imprinting in Organic Matrices 4 1.2.1 Covalent Approach 6 1.2.2 Non-Covalent Approach 7 1.2.3 Other Approaches for Organic MIP Fabrication 9 1.3 Molecular Imprinting in Inorganic Matrices 11 1.3.1 Sol-Gel Approach 12 1.3.2 Liquid Phase Deposition (LPD) Approach 15 1.4 Major Transducers 16 1.4.1 Mass-Sensitive Transducer 17 1.4.2 Electrochemical Transducer 19 1.4.3 Optical Transducer 21 1.5 Applications of Organic MIP Materials in Sensors 26 1.6 Applications of Inorganic MIP Materials in Sensors 31 1.6.1 Silica Based Imprinted Materials 31 1.6.2 Hybrid Imprinted Materials 38 1.6.3 LPD Based Imprinted Materials 40 1.6.4 Strategy for Improved Selectivity 43 1.7 Conclusions 45 2. Molecularly Imprinted Optical Sensing Receptor 65 Sing Muk Ng and Ramaier Narayanaswamy 2.1 Introduction 65 2.2 Chronological Protocols and Procedures 67 vi Contents 2.2.1 Selection of Materials and Ingredients 67 2.2.2 Polymerization Options 72 2.2.2.1 Free-radical initiated polymerization 72 2.2.2.2 Condensation polymerization 73 2.2.2.3 Electropolymerization 74 (cid:884)(cid:484)(cid:884)(cid:484)(cid:885)(cid:3) (cid:6)(cid:145)(cid:144)(cid:976)(cid:139)gurations of Matrix 75 2.2.3.1 Bulk 75 2.2.3.2 Monoliths 76 2.2.3.3 Membranes 77 2.2.4 Handling and Preparation 78 2.3 Rational Design of Receptors 79 2.3.1 Interaction Study of Pre-Polymerization Ingredients 79 2.3.2 Computational Modeling 81 2.3.3 Thermodynamic Considerations 83 2.3.4 Repeatability and Reproducibility 86 2.3.5 Commercialization 87 2.4 Optical Sensing Schemes and Transduction Systems 89 2.4.1 Direct Monitoring of Analyte 89 2.4.2 Direct Fluorescence 90 2.4.3 Displacement Assay 92 (cid:884)(cid:484)(cid:886)(cid:484)(cid:886)(cid:3) (cid:21)(cid:135)(cid:976)(cid:142)(cid:135)(cid:133)(cid:150)(cid:131)(cid:144)(cid:133)(cid:135)(cid:3)(cid:131)(cid:144)(cid:134)(cid:3)(cid:4)(cid:132)(cid:149)(cid:145)(cid:148)(cid:132)(cid:131)(cid:144)(cid:133)(cid:135)(cid:3) 94 2.4.5 Phosphorescence 96 2.4.6 Chemiluminescence 97 2.4.7 Surface Plasmon Resonance 98 2.4.8 Fluorescence Lifetime Decay 100 2.5 Advanced Probe Designs and Sensing (cid:6)(cid:145)(cid:144)(cid:976)(cid:139)(cid:137)(cid:151)(cid:148)(cid:131)(cid:150)(cid:139)(cid:145)(cid:144)(cid:3) (cid:883)02 2.5.1 Sensor Arrays 102 2.5.2 Optical MIP Chips 104 2.5.3 Micro- and Nano-sized Sensors 106 2.6 Binding Aspects and Analytical Signals 108 (cid:884)(cid:484)(cid:888)(cid:484)(cid:883)(cid:3) (cid:5)(cid:139)(cid:144)(cid:134)(cid:139)(cid:144)(cid:137)(cid:3)(cid:12)(cid:149)(cid:145)(cid:150)(cid:138)(cid:135)(cid:148)(cid:143)(cid:149)(cid:3)(cid:131)(cid:144)(cid:134)(cid:3)(cid:4)(cid:136)(cid:976)(cid:139)(cid:144)(cid:139)(cid:150)(cid:155)(cid:3) Distributions 108 2.6.2 Batch Binding Analysis and Binding Models 109 Contents vii 2.6.3 Correlation of Analytical Signal with Binding Isotherms Models 110 2.6.4 Advantage and Limitation 111 2.7 Summary 112 3. Translational Applications of Molecularly Imprinted Polymer-Based Electrochemical Sensors 119 Hung-Yin Lin, James L. Thomas, and Mei-Hwa Lee 3.1 Introduction 119 3.2 Principle of Molecularly Imprinted Polymers 121 3.2.1 Synthesis of MIPs 121 3.2.2 Characterization of MIPs 123 3.2.3 Morphology of MIPs 124 3.3 Transducers Employed with Molecularly Imprinted Polymers as Sensing Elements 126 3.3.1 Types of Transducers 126 3.3.2 Interface of Transducer and Molecularly Imprinted Polymers 130 3.3.3 Miniature MIPs-Based Sensors 130 3.3.4 Demonstration of MIPs-Based Electrochemical Sensors 134 3.4 Molecularly Imprinted Polymers-Based Sensors for the Real World 135 3.4.1 Source of Real Samples 135 3.4.2 Biomarkers 138 3.4.3 Cross-Talk Interference 138 3.5 Prospective 139 4. Optical Sensors for MonitoringTrace Inorganic Toxins 147 T. Prasada Rao, Dhanya James, and Milja T. Elias 4.1 Environmental Trace Analysis 148 4.2 Inorganic Toxins 148 4.3 Importance of Sampling in Trace Analysis 152 4.3.1 Sample Handling 152 4.3.2 Sample Pre-Treatment, Homogenization and Sub-Sampling 152 4.3.3 Sample Preparation 152 viii Contents 4.3.3.1 Decomposition of inorganic or organic matrices 153 4.3.3.2 Separation and pre-concentration steps 153 4.4 Trace/Ultra Trace Analytical Techniques 154 4.4.1 Selection of Analytical Technique/Method 157 4.4.2 Essential Features of Analytical Techniques 158 4.4.2.1 Signal processing, data handling and reporting 158 4.4.2.2 Signal integrity 158 4.4.2.3 Data handling 158 4.4.2.4 Good Automated Laboratory Practice (GALP) [1] 159 4.4.2.5 Reporting of results 159 4.5 Chemical Speciation 160 4.6 Sensors 161 4.6.1 Fundamentals of Optical Sensors (Optodes) 163 4.6.2 Optical Sensing of Ionic Analytes 163 4.6.3 Optical Sensing of Neutral Analytes 165 4.7 Molecularly Imprinted Polymers 166 4.7.1 Molecular Imprinting Technology 167 4.7.2 MIPs in Optical Sensing 168 4.8 Optical Sensors vis-a-vis Other Sensor Techniques 174 4.9 Future Outlook 174 5. MIP Thermistor 181 Rajagopal Rajkumar, Umporn Athikomrattanakul, Kristian Lettau, Martin Katterle, Bengt Danielsson, Axel Warsinke, Nenad Gajovic-Eichelmann, and Frieder W. Scheller 5.1 Introduction 181 5.1.1 The MIP Concept 181 5.1.2 MIP Sensors 183 5.1.3 Enzyme Thermistors 184 5.2 Covalently Imprinted Polymers Using Boronic Acid Derivates 188 5.2.1 Synthesis of Template (Fructosyl Valine) 189 Contents ix 5.2.2 Synthesis of Functional Monomer (Vinyl Phenyl Boroxine) 189 (cid:887)(cid:484)(cid:884)(cid:484)(cid:885)(cid:3) (cid:22)(cid:155)(cid:144)(cid:150)(cid:138)(cid:135)(cid:149)(cid:139)(cid:149)(cid:3)(cid:145)(cid:136)(cid:3)(cid:17)(cid:486)(cid:527)(cid:574)(cid:486)(cid:7)(cid:486)(cid:9)(cid:148)(cid:151)(cid:133)(cid:150)(cid:145)(cid:146)(cid:155)(cid:148)(cid:131)(cid:144)(cid:145)(cid:149)(cid:155)(cid:142)(cid:486)(cid:523)(cid:883)(cid:524)(cid:528)(cid:486) L-Valine2,3; 4,5-bis-O- ((4-Vinylphenyl) Boronate) 190 5.2.4 Synthesis of MIP and Control Polymers 190 5.2.5 MIP Thermistor Set-Up and Measurements 190 5.2.6 Thermometric MIP Sensor for Fructose 191 5.2.7 Thermometric MIP Sensor for Fructosyl Valine 193 5.2.8 Concentration Dependence of Fru-Val Binding 194 5.2.9 Closed Loop Studies 196 5.3 Non-Covalent MIPs Containing Two Functional Monomers for Carboxyphenyl Aminohydantoin (CPAH) as Analogon of Nitrofurantoin (NFT) 197 5.3.1 Synthesis of an Analogue Template, Carboxyphenyl Aminohydantoin (CPAH) 197 5.3.2 Synthesis of Functional Monomers 198 5.3.3 Preparation of MIPs Based on Two Functional Monomers 199 5.3.4 MIP-Based Thermometric Study 200 5.4 Bi-Functional Esterolytically Active MIP 203 5.4.1 Polymer Preparation 204 5.4.2 Thermometric Characterization of Adsorption and Catalysis 205 5.5 Conclusions 209 Part 2 Potential Materials for Molecular Imprinting 217 6. The Use of a Thermally Reversible Bond for Molecular Imprinting 219 Ji Young Chang 6.1 Introduction 219 6.2 Cross-Linked Vinyl Polymer Matrix 221 6.3 Silica Matrix 226 6.4 Polyimide as Noncross-Linked Matrix 228 6.5 Summary and Outlook 232