Nanofabrication Towards Biomedical Applications Techniques, Tools, Applications, and Impact Edited by C S S R Kumar, J Hormes, C Leuschner Editors Dr Challa S S R Kumar Center for Advanced Microstructures and Devices Louisiana State University 6980 Jefferson Highway Baton Rouge, LA 70806 USA ckumar1@lsu.edu Prof Dr Josef Hormes Center for Advanced Microstructures and Devices Louisiana State University 6980 Jefferson Highway Baton Rouge, LA 70806 USA hormes@lsu.edu Prof Dr Carola Leuschner Reproductive Biotechnology Laboratory Pennington Biomedical Research Centre Louisiana State University 6400 Perkins Road Baton Rouge, LA 70808 USA leuschc@pbrc.edu & All books published by Wiley-VCH are carefully produced Nevertheless, authors, editors, and publisher not warrant the information contained in these books, including this book, to be free of errors Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at  2005 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 – nor transmitted or translated into machine language without written permission from the publishers Registered names, trademarks, etc used in this book, even when not specifically marked as such, are not to be considered unprotected by law Printed in the Federal Republic of Germany Printed on acid-free paper Typesetting Kühn & Weyh, Satz und Medien, Freiburg Printing Strauss GmbH, Mörlenbach Bookbinding Litges & Dopf Buchbinderei GmbH, Heppenheim ISBN-13 978-3-527-31115-6 ISBN-10 3-527-31115-7 V Foreword Nanobiotechnology: Hype, Hope and the Next Small Thing is the title of one of the chapters in this book This title suggests that the applications of nanotechnology in biology and medicine are still in a somewhat uncertain future, but the contrary is also true: there are already several products, such as zinc oxide nanoparticles in sun cream or nano-silver as a coating material for home appliances to destroy bacteria and prevent them from spreading, that are available on the market Other, even more exciting applications are in the testing phase, for example, using magnetic nanoparticles for a targeted hyperthermia treatment of brain cancer There are of course also applications that might become reality in the far future – though there are always surprises possible in nanotechnology, e.g., implantable pumps the size of a molecule that deliver medicines with a precise dose when and where needed, or the possibility to remove a damaged part of a cell and replacing it with a biological machine These applications are some of the goals stated in the National Institute of Health roadmap for nanomedicine, which was established in spring 2003 This initiative is again part of a larger US National Nanotechnology Initiative (NNI), for which the President's budget will provide about $1 bn for 2005 for projects coordinated by at least ten different federal agencies The book aptly named Nanofabrication Towards Biomedical Applications is timely as the contributions are all written by experts in their field, summarizing the present status of influence of nanotechnology in biology, biotechnology, medicine, education, economy, society and industry I am particularly impressed with the judicious combination of chapters covering technical aspects of the various fields of nanobiology and nanomedicine from synthesis and characterization of nanosystems to practical applications, and the societal and educational impact of the emerging new technologies Thus, this book gives an excellent overview for non-specialists by providing an up-to-date review of the existing literature in addition to providing new insights for interested scientists, giving a jump-start into this emerging research area I hope this book will stimulate many scientists to start research in these exciting and important directions I am particularly pleased to recognize the efforts of Nanofabrication Towards Biomedical Applications C S S R Kumar, J Hormes, C Leuschner (Eds.) Copyright  2005 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN 3-527-31115-7 VI Foreword the Center for Advanced Microstructures and Devices (CAMD) and of the Pennington Biomedical Research Center (PBRC) in taking a lead to spread the influence of biomedical nanotechnology, and I am convinced that the book will be a valuable tool in the hands of all those interested in discovering new paths and opportunities in this fascinating new field William L Jenkins President, Louisiana State University VII Contents Preface XV List of Contributors XVIII I Fabrication of Nanomaterials Synthetic Approaches to Metallic Nanomaterials Ryan Richards and Helmut Bönnemann 1.1 1.2 1.3 1.4 1.5 1.6 1.7 Introduction Wet Chemical Preparations Reducing Agents Electrochemical Synthesis 14 Decomposition of Low-Valency Transition Metal Complexes Particle Size Separations 18 Potential Applications in Materials Science 20 Synthetic Approaches for Carbon Nanotubes 33 Bingqing Wei, Robert Vajtai, and Pulickel M Ajayan 2.1 2.1.1 2.1.2 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.2.6 2.3 2.3.1 2.3.2 2.3.3 Introduction 33 Structure of Carbon Nanomaterials 33 Wide Range of Properties 34 Family of Carbon Nanomaterials 35 Fullerenes 35 Carbon Onions (Nested Fullerenes) 36 Carbon Nanofibers 38 Carbon Nanotubes 39 Nanoscale Diamonds and Diamond-Like Carbon 41 Nanoporous Activated Carbon 42 Synthesis of Carbon Nanotubes 43 Nanotube Growth via the Arc-Discharge Method 43 Carbon Nanotubes Produced by Laser Ablation 44 Chemical Vapor Deposition as a Tool for Carbon Nanotube Production 45 17 Nanofabrication Towards Biomedical Applications C S S R Kumar, J Hormes, C Leuschner (Eds.) Copyright  2005 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN 3-527-31115-7 VIII Contents 2.4 2.4.1 2.4.2 2.4.3 2.5 2.5.1 2.5.2 2.6 Controllable Synthesis of Carbon Nanotube Architectures Substrate-Site-Selective Growth 46 Three-Dimensional Nanotube Architectures 47 Super-Long SWNT Strands 48 Perspective on Biomedical Applications 49 Imaging and Diagnostics 49 Biosensors 50 Conclusion 52 Nanostructured Systems from Low-Dimensional Building Blocks Donghai Wang, Maria P Gil, Guang Lu, and Yunfeng Lu 3.1 3.2 3.2.1 3.2.1.1 3.2.1.2 3.2.2 3.3 3.3.1 3.3.1.1 3.3.1.2 3.3.1.3 3.3.2 3.4 3.4.1 3.4.1.1 3.4.1.2 3.4.2 3.5 3.5.1 3.5.2 3.5.3 3.5.4 3.6 3.6.1 3.6.1.1 3.6.1.2 3.6.2 3.6.2.1 3.6.2.2 3.7 3.7.1 3.7.1.1 3.7.1.2 3.7.1.3 Introduction 57 Nanostructured System by Self-Assembly 58 Nanoparticle Assemblies 58 Role of Capping Molecules 58 Multicomponent Assembly 60 1D Nanostructure Assemblies 61 Biomimetic and Biomolecular Recognition Assembly 62 Assembly by Biomolecular Recognition 62 DNA-Assisted Assembly 62 Protein-Assisted Assemblies 63 Virus-Assisted Assemblies 64 Biomimetic Assembly Process 65 Template-Assisted Integration and Assembly 67 Template-Assisted Self-Assembly 67 Templating with Relief Structures 67 Templating with Functionalized Patterned Surfaces 69 Patterning of Nanoscale Component Assemblies 69 External-Field-Induced Assembly 70 Flow-Directed Assembly 70 Electric-Field-Induced Assembly 71 Electrophoretic Assembly 71 Assembly Using Langmuir–Blodgett Techniques 72 Direct Synthesis of 2D/3D Nanostructure 73 Templated Synthesis 73 Mesoporous Silica-Templated Synthesis 74 Direct Nanostructures Synthesis Using Soft Templates 76 Direct Synthesis of Oriented 1D Nanostructure Arrays 78 Oriented Arrays by Chemical Vapor Deposition 78 Seeded Solution Growth 79 Applications 81 Chemical and Biological Sensing Applications 81 Carbon-Nanotube-Based Sensing 81 Semiconducting-Nanowire-Based Sensing 82 Metallic-Nanowire-Based Sensing 83 45 57 Contents 3.7.2 3.8 Other Applications of Integrated Nanoscale Component Assemblies Concluding Remarks 85 Nanostructured Collagen Mimics in Tissue Engineering Sergey E Paramonov and Jeffrey D Hartgerink 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 Introduction 95 Collagen Structural Hierarchy 96 Amino Acid Sequence and Secondary Structure 97 Experimental Observation of the Collagen Triple Helix 99 Folding Kinetics 101 Stabilization Through Sequence Selection 102 Stabilization via Hydroxyproline: The Pyrrolidine Ring Pucker 104 Triple Helix Stabilization Through Forced Aggregation 106 Extracellular Matrix and Collagen Mimics in Tissue Engineering 108 Sticky Ends and Supramolecular Polymerization 110 Conclusion 114 Molecular Biomimetics: Building Materials Natures Way, One Molecule at a Time 119 Candan Tamerler and Mehmet Sarikaya 5.1 5.2 5.3 5.4 5.4.1 5.4.2 5.4.3 5.5 Introduction 119 Inorganic Binding Peptides via Combinatorial Biology 122 Physical Specificity and Molecular Modeling 124 Applications of Engineered Polypeptides as Molecular Erectors 125 Self-Assembly of Inorganic-Binding Polypeptides as Monolayers 126 Morphogenesis of Inorganic Nanoparticles via GEPIs 127 Assembly of Inorganic Nanoparticles via GEPIs 128 Future Prospects and Potential Applications in Nanotechnology 129 II Characterization Tools for Nanomaterials and Nanosystems Electron Microscopy Techniques for Characterization of Nanomaterials Jian-Min (Jim) Zuo 6.1 6.2 6.2.1 6.2.2 6.2.3 6.3 6.3.1 6.3.2 6.4 6.5 Introduction 137 Electron Diffraction and Geometry 138 Selected-Area Electron Diffraction 139 Nano-Area Electron Diffraction 139 Convergent-Beam Electron Diffraction 141 Theory of Electron Diffraction 142 Kinematic Electron Diffraction and Electron Atomic Scattering 142 Kinematical Electron Diffraction from an Assembly of Atoms 144 High-Resolution Electron Microscopy 147 Experimental Analysis 151 83 95 135 137 IX X Contents 6.5.1 6.5.2 6.5.3 6.6 6.6.1 6.6.2 6.7 Experimental Diffraction Pattern Recording 151 The Phase Problem and Inversion 152 Electron Diffraction Oversampling and Phase Retrieval for Nanomaterials 153 Applications 156 Structure Determination of Individual Single-Wall Carbon Nanotubes 156 Structure of Supported Small Nanoclusters and Epitaxy 158 Conclusions and Future Perspectives 160 X-Ray Methods for the Characterization of Nanoparticles Hartwig Modrow 7.1 7.2 7.3 Introduction 163 X-Ray Diffraction: Getting to Know the Arrangement of Atoms 164 Small-Angle X-Ray Scattering: Learning About Particle Shape and Morphology 169 X-Ray Absorption: Exploring Chemical Composition and Local Structure 172 Applications 176 Co Nanoparticles with Varying Protection Shells 176 PdxPty Nanoparticles 180 Formation of Pt Nanoparticles 183 Summary and Conclusions 186 General Approach 187 X-Ray Diffraction 188 Small-Angle Scattering 189 X-Ray Absorption 190 7.4 7.5 7.5.1 7.5.2 7.5.3 7.6 A.1 A.2 A.3 A.4 163 Single-Molecule Detection and Manipulation in Nanotechnology and Biology 197 Christopher L Kuyper, Gavin D M Jeffries, Robert M Lorenz, and Daniel T Chiu 8.1 8.2 8.2.1 Introduction 197 Optical Detection of Single Molecules 198 Detecting Single Molecules with Confocal Fluorescence Microscopy 198 Visualizing Single Molecules with Epifluorescence Detection 200 Total Internal-Reflection Fluorescence (TIRF) Microscopy 201 Single-Molecule Surface-Enhanced Resonance Raman Spectroscopy 202 Single-Molecule Manipulations Using Optical Traps 203 Force Studies Using Single-Beam Gradient Traps 203 Optical Vortex Trapping 205 Optical Arrays 206 8.2.2 8.2.3 8.2.4 8.3 8.3.1 8.3.2 8.3.3 Contents 8.4 8.4.1 8.4.2 8.4.3 8.4.4 8.5 8.5.1 8.5.2 8.6 8.7 Applications in Single-Molecule Spectroscopy 207 Conformational Dynamics of Single DNA Molecules in Solution 207 Probing the Kinetics of Single Enzyme Molecules 209 Single-Molecule DNA Detection, Sorting, and Sequencing 211 Single-Molecule Imaging in Living Cells 213 Single-Molecule Detection with Bright Fluorescent Species 214 Optical Probes 214 Quantum Dots 215 Nanoscale Chemistry with Vesicles and Microdroplets 215 Perspectives 217 Nanotechnologies for Cellular and Molecular Imaging by MRI 227 Patrick M Winter, Shelton D Caruthers, Samuel A Wickline, and Gregory M Lanza 9.1 9.2 9.3 9.4 9.5 9.5.1 9.5.2 9.5.3 9.6 Introduction 227 Cardiovascular Disease 228 Cellular and Molecular Imaging 229 Cellular Imaging with Iron Oxides 233 Molecular Imaging with Paramagnetic Nanoparticles Optimization of Formulation Chemistry 236 Optimization of MRI Techniques 240 In Vivo Molecular Imaging of Angiogenesis 242 Conclusions 245 III Application of Nanotechnology in Biomedical Research 10 Nanotechnology in Nonviral Gene Delivery 253 Latha M Santhakumaran, Alex Chen, C K S Pillai, Thresia Thomas, Huixin He, and T J Thomas 10.1 10.2 10.2.1 10.2.2 10.2.3 10.2.4 10.2.5 10.2.6 10.3 10.3.1 10.3.2 10.3.3 10.3.3.1 10.3.3.2 Introduction 253 Agents That Provoke DNA Nanoparticle Formation Polyamines 255 Cationic Lipids 259 Polyethylenimine 260 Dendrimers 262 Proteins and Polypeptides 265 Polymers 267 Characterization of DNA Nanoparticles 267 Laser Light Scattering 268 Electron Microscopy 269 Atomic Force Microscopy 271 DNA Nanoparticle Studies by AFM 272 Limitation of AFM Technique 274 234 251 255 XI ... tools for biomedical fields We, therefore, designed the contents of the Nanofabrication Towards Biomedical Applications C S S R Kumar, J Hormes, C Leuschner (Eds.) Copyright  2005 WILEY- VCH... particularly pleased to recognize the efforts of Nanofabrication Towards Biomedical Applications C S S R Kumar, J Hormes, C Leuschner (Eds.) Copyright  2005 WILEY- VCH Verlag GmbH & Co KGaA, Weinheim... Tool for Carbon Nanotube Production 45 17 Nanofabrication Towards Biomedical Applications C S S R Kumar, J Hormes, C Leuschner (Eds.) Copyright  2005 WILEY- VCH Verlag GmbH & Co KGaA, Weinheim