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Edited by David T. Pierce and Julia Xiaojun Zhao Trace Analysis with Nanomaterials Related Titles Blackledge, R. D. (ed.) Hillenkamp, F., Peter-Katalinic, J. (eds.) Forensic Analysis on MALDI MS the Cutting Edge A Practical Guide to Instrumentation, New Methods for Trace Methods and Applications Evidence Analysis 2007 2007 ISBN: 978-3-527-31440-9 ISBN: 978-0-471-71644-0 Schalley, C. A. (ed.) Xu, X.-H. N. (ed.) Analytical Methods in New Frontiers in Supramolecular Chemistry Ultrasensitive Bioanalysis 2007 Advanced Analytical Chemistry ISBN: 978-3-527-31505-5 Applications in Nanobiotechnology, Single Molecule Detection, and Single Cell Analysis 2007 E-Book ISBN: 978-0-470-11949-5 Otto, M. Chemometrics Statistics and Computer Application in Analytical Chemistry 2007 ISBN: 978-3-527-31418-8 Edited by David T. Pierce and Julia Xiaojun Zhao Trace Analysis with Nanomaterials The Editors All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and Dr. David T. Pierce publisher do not warrant the information contained University of North Dakota in these books, including this book, to be free of Department of Chemistry errors. Readers are advised to keep in mind that 151 Cornell Street, Stop 9024 statements, data, illustrations, procedural details or Grand Forks, ND 58202-9024 other items may inadvertently be inaccurate. USA Library of Congress Card No.: applied for Dr. Julia Xiaojun Zhao University of North Dakota British Library Cataloguing-in-Publication Data Department of Chemistry A catalogue record for this book is available from 151 Cornell Street, Stop 9024 the British Library. Grand Forks, ND 58202-9024 USA Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografi e; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfi lm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifi cally marked as such, are not to be considered unprotected by law. Composition Toppan Best-set Premedia Limited, Hong Kong Printing and Bookbinding Strauss GmbH, Mörlenbach Cover Design Adam Design, Weinheim Printed in the Federal Republic of Germany Printed on acid-free paper ISBN: 978-3-527-32350-0 V Contents Preface XIII List of Contributors XVII Part 1 Biological and Chemical Analysis 1 1 Photoswitchable Nanoprobes for Biological Imaging Applications 3 Zhiyuan Tian, Wuwei Wu, and Alexander D.Q. Li 1.1 Introduction 3 1.2 Photoswitchable Fluorescent Nanoprobes 4 1.2.1 Single-Color (On-Off ) Fluorescent Nanoprobes 5 1.2.1.1 Fluorescence Modulation of Semiconductor Nanocrystals 5 1.2.1.2 Isomerization of Photochromic Spiropyrans 7 1.2.1.3 Isomerization of Photochromic Diarylethenes 9 1.2.1.4 Structural Conversion of a Photoswitchable Protein 11 1.2.2 Dual-Color Fluorescence Nanoprobes 13 1.2.2.1 Green to Red Fluorescence Conversion with Proteins 13 1.2.2.2 FRET-Based Fluorescence Photoswitching 15 1.2.2.3 Photoswitchable Nanoparticles Based on a Single Dye 17 1.2.3 Photoswitchable Fluorescent Nanoparticles for Bioimaging 19 1.3 Photoswitchable Magnetic Nanoparticles 22 1.3.1 Nanoparticles with Photoswitchable Magnetization 22 1.3.2 Magnetic Nanoparticles with Photoswitchable Fluorescence 24 1.4 Future Perspectives 25 Acknowledgments 26 References 26 2 Applications of Semiconductor Quantum Dots in Chemical and Biological Analysis 31 Xingguang Su and Qiang Ma 2.1 Introduction 31 2.2 History 32 2.3 Classifi cations 32 Trace Analysis with Nanomaterials. Edited by David T. Pierce and Julia Xiaojun Zhao Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32350-0 VI Contents 2.3.1 II–VI Quantum Dots 32 2.3.2 III–V Quantum Dots 33 2.3.3 IV–VI Quantum Dots 34 2.3.4 Core–Shell Quantum Dots 34 2.3.5 Alloyed Quantum Dots 35 2.4 Characteristics 35 2.4.1 Electronic Properties 36 2.4.2 Unique Optical Properties 38 2.5 Synthesis and Surface Chemistry 40 2.5.1 Organometallic Approaches 40 2.5.2 Aqueous Phase Colloidal Synthesis 41 2.5.3 Modifi cation of Surface Chemistry 41 2.6 Trace Analysis Using Quantum Dots 42 2.6.1 Determinations Based on Direct Fluorescence Response 42 2.6.2 Fluorescence Resonance Energy Transfer (FRET) Analysis Using QDs 44 2.6.3 Room-Temperature Phosphorescence Detection 45 2.6.4 Near-Infrared Detection Using QDs 46 2.6.5 Rayleigh Light Scattering (RLS) Analysis 48 2.6.6 Chemiluminescence Analysis 48 2.6.7 Electrochemical Analysis 50 2.6.8 Chemosensors and Biosensors 51 2.6.9 “Nano-On-Micro” Assay 52 2.7 Summary 54 Acknowledgments 55 References 55 3 Nanomaterial-Based Electrochemical Biosensors and Bioassays 61 Guodong Liu, Xun Mao, Anant Gurung, Meenu Baloda, Yuehe Lin, and Yuqing He 3.1 Introduction 61 3.2 Nanomaterial Labels Used in Electrochemical Biosensors and Bioassays 63 3.2.1 Metal Nanoparticles 63 3.2.1.1 Metal NP Labels for Electrochemical Detection of DNA 64 3.2.1.2 Metal NP Labels for Electrochemical Immunoassays and Immunosensors 68 3.2.2 Semiconductor Nanoparticles 70 3.2.2.1 QD Labels for Electrochemical Detection of DNA 70 3.2.2.2 QD Labels for Electrochemical Immunoassay 72 3.2.3 Carbon Nanotubes 73 3.2.4 Apoferritin Nanovehicles 75 3.2.5 Liposomes 77 3.2.6 Silica Nanoparticles 79 3.2.7 Nanowires and Nanorods 81 3.3 Nanomaterial-Based Electrochemical Devices for Point-of-Care Diagnosis 82 Contents VII 3.4 Conclusions 84 Acknowledgments 85 References 85 4 Chemical and Biological Sensing by Electron Transport in Nanomaterials 89 Jai-Pil Choi 4.1 Introduction 89 4.2 Electron Transport through Metal Nanoparticles 90 4.2.1 Coulomb Blockade Effect and Single Electron Transfer 91 4.2.2 Voltammetry of Metal Nanoparticles in Solutions 92 4.2.3 Electron Transport through Metal Nanoparticle Assemblies 95 4.3 Sensing Applications Based on Electron Transport in Nanoparticle Assemblies 97 4.3.1 Chemical Sensors 97 4.3.1.1 Sensors Based on Metal Nanoparticle Films 98 4.3.1.2 Sensors Based on Semiconducting Oxide Nanoparticles 101 4.3.2 Biosensors 103 4.4 Concluding Remarks 106 Acknowledgments 107 References 108 5 Micro- and Nanofl uidic Systems for Trace Analysis of Biological Samples 111 Debashis Dutta 5.1 Introduction 111 5.2 Nucleic Acid Analysis 112 5.2.1 Miniaturization of PCR Devices 112 5.2.2 Integration of PCR with Separation, DNA Hybridization, and Sample Preparation 115 5.2.3 Novel Micro- and Nanofl uidic Tools for DNA Analysis 116 5.3 Protein Analysis 118 5.3.1 Protein Separations 118 5.3.2 On-Chip Protein Pre-concentration 121 5.3.3 Integrated Microfl uidic Devices for Protein Analysis 122 5.4 Microfl uidic Devices for Single-Cell Analysis 123 5.5 Conclusion 127 References 128 Part 2 Environmental Analysis 133 6 Molecularly Imprinted Polymer Submicron Particles Tailored for Extraction of Trace Estrogens in Water 135 Edward Lai, Anastasiya Dzhun, and Zack De Maleki 6.1 Introduction 135 6.2 Principle of Molecular Recognition by Imprinting 138 VIII Contents 6.2.1 Monomers, Crosslinkers, and Porogen Solvents 139 6.2.2 Rebinding of Target Analytes 140 6.2.3 Computational Modeling 141 6.3 Analytical Application of MIPs for Biopharmaceuticals and Toxins 143 6.4 Preparation of MIP Submicron Particles 146 6.5 Binding Properties of MIP Submicron Particles with E2 148 6.5.1 Models of E2 Binding with MIP Submicron Particles 149 6.5.2 Kinetics of MIP Binding with E2 150 6.6 Trace Analysis of E2 in Wastewater Treatment 150 6.7 Current Progress 152 6.8 Recent Advances in MIP Technology for Continuing Development 153 Acknowledgments 156 References 156 7 Trace Detection of High Explosives with Nanomaterials 161 Wujian Miao, Cunwang Ge, Suman Parajuli, Jian Shi, and Xiaohui Jing 7.1 Introduction 161 7.2 Techniques for Trace Detection of High Explosives 164 7.2.1 Electrochemical Sensors 164 7.2.1.1 Nanomaterial Modifi ed Electrodes 165 7.2.1.2 “Artifi cial Peroxidase”-Modifi ed Electrodes Based on Prussian Blue 166 7.2.2 Electrogenerated Chemiluminescence 167 7.2.3 Fluorescence-Based Sensors 169 7.2.3.1 Quenching Sensors Based on Fluorescent Polymer Porous Films 169 7.2.3.2 Quenching Sensors Based on Fluorescent Nanofi bril Films 171 7.2.3.3 Quenching Sensors Based on Quantum Dots 172 7.2.3.4 Quenching Sensors Based on Organic Supernanostructures 175 7.2.3.5 Fluoroimmunoassays Using QD-Antibody Conjugates 176 7.2.3.6 Displacement Immunosensors 176 7.2.4 Microcantilever Sensors 178 7.2.5 Metal Oxide Semiconductor (MOS) Nanoparticle Gas Sensors 180 7.2.6 Surface-Enhanced Ramam Scattering Spectroscopy 180 7.3 Conclusions 181 Acknowledgments 182 References 182 8 Nanostructured Materials for Selective Collection of Trace-Level Metals from Aqueous Systems 191 Sean A. Fontenot, Timothy G. Carter, Darren W. Johnson, R. Shane Addleman, Marvin G. Warner, Wassana Yantasee, Cynthia L. Warner, Glen E. Fryxell, and John T. Bays 8.1 Introduction 191 8.2 Sorbents for Trace-Metal Collection and Analysis: Relevant Figures of Merit 192 Contents IX 8.3 Thiol-Functionalized Ordered Mesoporous Silica for Heavy Metal Collection 194 8.3.1 Performance Comparisons of Sorption Materials for Environmental Samples 194 8.3.2 Performance Comparisons of Sorption Materials for Biological Samples 197 8.4 Surface-Functionalized Magnetic Nanoparticles for Heavy Metal Capture and Detection 200 8.5 Nanoporous Carbon Based Sorbent Materials 206 8.5.1 Chemically-Modifi ed Activated Carbons 207 8.5.2 Templated Mesoporous Carbons 209 8.6 Other Nanostructured Sorbent Materials 212 8.6.1 Zeolites 212 8.6.2 Ion-Imprinted Polymers 214 8.7 Concluding Thoughts 215 Acknowledgments 217 References 217 9 Synthesis and Analysis Applications of TiO2-Based Nanomaterials 223 Aize Li, Benjamen C.