V Contents Preface XIII List of Contributors XVII 1 Polymer Thin Films for Biomedical Applications 1 Venkat K. Vendra, Lin Wu, and Sitaraman Krishnan 1.1 Introduction 1 1.2 Biocompatible Coatings 2 1.2.1 Protein-Repellant Coatings 2 1.2.1.1 PEGylated Thin Films 2 1.2.1.2 Non-PEGylated Hydrophilic Thin Films 3 1.2.1.3 Thin Films of Hyperbranched Polymers 4 1.2.1.4 Multilayer Thin Films 5 1.2.2 Antithrombogenic Coatings 6 1.2.2.1 Surface Chemistry and Blood Compatibility 6 1.2.2.2 Membrane-Mimetic Thin Films 7 1.2.2.3 Heparin-Mimetic Thin Films 8 1.2.2.4 Clot-Lyzing Thin Films 8 1.2.2.5 Polyelectrolyte Multilayer Thin Films 9 1.2.2.6 Polyurethane Coatings 9 1.2.2.7 Vapor-Deposited Thin Films 10 1.2.3 Antimicrobial Coatings 10 1.2.3.1 Cationic Polymers 10 1.2.3.2 Nanocomposite Polymer Thin Films Incorporating Inorganic Biocides 11 1.2.3.3 Antibiotic-Conjugated Polymer Thin Films 12 1.2.3.4 Biomimetic Antibacterial Coatings 13 1.2.3.5 Thin Films Resistant to the Adhesion of Viable Bacteria 13 1.3 Coatings for Tissue Engineering Substrates 14 1.3.1 PEGylated Thin Films 15 1.3.2 Zwitterionic Thin Films 15 1.3.3 Thin Films of Hyperbranched Polymers 16 1.3.4 Polyurethane Coatings 17 1.3.5 Polysaccharide-Based Thin Films 18 Nanomaterials for the Life Sciences Vol.5: Nanostructured Thin Films and Surfaces. Edited by Challa S. S. R. Kumar Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32155-1 VI Contents 1.3.6 Polyelectrolyte Multilayer Thin Films 18 1.3.7 Temperature-Responsive Polymer Coatings 25 1.3.8 Electroactive Thin Films 27 1.3.9 Other Functional Polymer Coatings 28 1.3.10 Multilayer Thin Films for Cell Encapsulation 30 1.3.11 Patterned Thin Films 31 1.4 Polymer Thin Films for Drug Delivery 33 1.5 Polymer Thin Films for Gene Delivery 36 1.6 Conclusions 39 References 39 2 Biofunctionalization of Polymeric Thin Films and Surfaces 55 Holger Schönherr 2.1 Introduction: The Case of Biofunctionalized Surfaces and Interfaces 55 2.2 Polymer-Based Biointerfaces 58 2.2.1 Requirements for Biofunctionalized Polymer Surfaces 58 2.2.2 Surface Modifi cation Using Functional Polymers and Polymer-Based Approaches 63 2.2.2.1 Grafting of Polymers to Surfaces 64 2.2.2.2 Polymer Brushes by Surface-Initiated Polymerization 66 2.2.2.3 Physisorbed Multifunctional Polymers 72 2.2.2.4 Multipotent Covalent Coatings 74 2.2.2.5 Plasma Polymerization and Chemical Vapor Deposition (CVD) Approaches 75 2.2.3 Surface Modifi cation of Polymer Surfaces, and Selected Examples 79 2.2.3.1 Coupling and Bioconjugation Strategies 79 2.2.3.2 Interaction with Cells 86 2.2.3.3 Patterned Polymeric Thin Films in Biosensor Applications 89 2.3 Summary and Future Perspectives 91 References 92 3 Stimuli-Responsive Polymer Nanocoatings 103 Ana L. Cordeiro 3.1 Introduction 103 3.2 Stimuli-Responsive Polymers 105 3.2.1 Polymers Responsive to Temperature 105 3.2.2 Polymers Responsive to pH 107 3.2.3 Dual Responsive/Multiresponsive Polymers 108 3.2.4 Intelligent Bioconjugates 109 3.2.5 Responsive Biopolymers 110 3.3 Polymer Films and Interfacial Analysis 112 3.4 Applications 114 3.4.1 Release Matrices 114 3.4.2 Cell Sheet Engineering 115 Contents VII 3.4.3 Biofi lm Control 122 3.4.4 Cell Sorting 123 3.4.5 Stimuli-Modulated Membranes 123 3.4.6 Chromatography 124 3.4.7 Microfl uidics and Laboratory-on-a-Chip 128 3.5 Summary and Future Perspectives 130 Acknowledgments 131 References 131 4 Ceramic Nanocoatings and Their Applications in the Life Sciences 149 Eng San Thian 4.1 Introduction 149 4.2 Magnetron Sputtering 150 4.3 Physical and Chemical Properties of SiHA Coatings 151 4.4 Biological Properties of SiHA Coatings 154 4.4.1 In Vitro Acellular Testing 154 4.4.2 In Vitro Cellular Testing 160 4.5 Future Perspectives 168 4.6 Conclusions 170 References 171 5 Gold Nanofi lms: Synthesis, Characterization, and Potential Biomedical Applications 175 Shiho Tokonami, Hiroshi Shiigi, and Tsutomu Nagaoka 5.1 Introduction 175 5.2 Preparation of Various AuNPs 177 5.3 Functionalization of AuNPs and their Applications through Aggregation 178 5.4 AuNP Assemblies and Arrays 182 5.4.1 AuNP Assemblies Structured on Substrates 182 5.4.2 AuNP Assembly on Biotemplates 184 5.4.3 AuNP Arrays for Gas Sensing 186 5.4.4 AuNP Arrays for Biosensing 188 5.5 Conclusions 195 References 195 6 Thin Films on Titania, and Their Applications in the Life Sciences 203 Izabella Brand and Martina Nullmeier 6.1 Introduction 203 6.2 Titanium in Contact with a Biomaterial 204 6.3 Lipid Bilayers at the Titania Surface 206 6.3.1 Formation of Lipid Bilayers on the Titania Surface 207 6.3.1.1 Spreading of Vesicles on a TiO Surface: Comparison to a SiO 2 2 Surface 207 VIII Contents 6.3.2 Interactions: Lipid Molecule–Titania Surface 213 6.3.3 Structure and Conformation of Lipid Molecules in the Bilayer on the Titania Surface 216 6.3.3.1 Structure of Phosphatidylcholine on the Titania Surface 217 6.4 Characteristics of Extracellular Matrix Proteins on the Titania Surface 226 6.4.1 Collagen Adsorption on Titania Surfaces 227 6.4.1.1 Morphology of Collagen Adsorbed on an Oxidized Titanium Surface 228 6.4.1.2 Adsorption of Collagen on a Hydroxylated Titania Surface 228 6.4.1.3 Morphology and Structure of Collagen Adsorbed on a Calcifi ed Titania Surface 229 6.4.1.4 Conclusions 231 6.4.1.5 Structure of Collagen on the Titania Surface: Theoretical Predictions 232 6.4.2 Fibronectin Adsorption on the Titania Surface 234 6.4.2.1 Morphology of Fibronectin Adsorbed on the Titania Surface 235 6.4.2.2 Fibronectin–Titania Interactions 236 6.4.2.3 Structure of Fibronectin Adsorbed onto the Titania Surface 238 6.4.2.4 Atomic-Scale Picture of Fibronectin Adsorbed on the Titania Surface: Theoretical Predictions 240 6.4.2.5 Conclusions 241 6.5 Conclusions 242 Acknowledgments 244 References 244 7 Preparation, Characterization, and Potential Biomedical Applications of Nanostructured Zirconia Coatings and Films 251 Xuanyong Liu, Ying Xu, and Paul K. Chu 7.1 Introduction 251 7.2 Preparation and Characterization of Nano-ZrO Films 251 2 7.2.1 Cathodic Arc Plasma Deposition 251 7.2.2 Plasma Spraying 254 7.2.3 Sol–Gel Methods 255 7.2.4 Electrochemical Deposition 257 7.2.5 Anodic Oxidation and Micro-Arc Oxidation 260 7.2.6 Magnetron Sputtering 262 7.3 Bioactivity of Nano-ZrO Coatings and Films 263 2 7.4 Cell Behavior on Nano-ZrO Coatings and Films 267 2 7.5 Applications of Nano-ZrO Films to Biosensors 269 2 References 273 8 Free-Standing Nanostructured Thin Films 277 Izumi Ichinose 8.1 Introduction 277 8.2 The Roles of Free-Standing Thin Films 277 Contents IX 8.2.1 Films as Partitions 277 8.2.2 Nanoseparation Membranes 279 8.2.3 Biomembranes 281 8.3 Free-Standing Thin Films with Bilayer Structures 282 8.3.1 Supported Lipid Bilayers and “Black Lipid Membranes” 282 8.3.2 Foam Films and Newton Black Films 283 8.3.3 Dried Foam Film 284 8.3.4 Foam Films of Ionic Liquids 286 8.4 Free-Standing Thin Films Prepared with Solid Surfaces 289 8.5 Free-Standing Thin Films of Nanoparticles 290 8.6 Nanofi brous Free-Standing Thin Films 292 8.6.1 Electrospinning and Filtration Methods 292 8.6.2 Metal Hydroxide Nanostrands 293 8.6.3 Nanofi brous Composite Films 295 8.6.4 Nanoseparation Membranes 298 8.7 Conclusions 299 References 300 9 Dip-Pen Nanolithography of Nanostructured Thin Films for the Life Sciences 303 Euiseok Kim, Yuan-Shin Lee, Ravi Aggarwal, and Roger J. Narayan 9.1 Introduction 303 9.2 Dip-Pen Nanolithography 304 9.2.1 Important Parameters 305 9.2.2 Applications of DPN 306 9.3 Direct and Indirect Patterning of Biomaterials Using DPN 310 9.3.1 Background 310 9.3.2 Direct Patterning 311 9.3.3 Indirect Patterning 314 9.4 Applications of DPN for Medical Diagnostics and Drug Development 316 9.4.1 General Methods of Nano/Micro Bioarray Patterning 317 9.4.2 Virus Array Generation and Detection Tests 318 9.4.3 Diagnosis of Allergic Disease 320 9.4.4 Cancer Detection Using Nano/Micro Protein Arrays 321 9.4.5 Drug Development 323 9.4.6 Lab-on-a-Chip Using Microarrays 323 9.5 Summary and Future Directions 325 References 325 10 Understanding and Controlling Wetting Phenomena at the Micro- and Nanoscales 331 Zuankai Wang and Nikhil Koratkar 10.1 Introduction 331 10.2 Wetting and Contact Angle 333 10.3 Design and Creation of Superhydrophobic Surfaces 335 X Contents 10.3.1 Design Parameters for a Robust Composite Interface 335 10.3.2 Creation of Superhydrophobic Surfaces 335 10.3.3 Superhydrophobic Surfaces with Unitary Roughness 336 10.3.4 Superhydrophobic Surfaces with Two-Scale Roughness 336 10.3.5 Superhydrophobic Surfaces with Reentrant Structure 338 10.4 Impact Dynamics of Water on Superhydrophobic Surfaces 339 10.4.1 Impact Dynamics on Nanostructured MWNT Surfaces 340 10.4.2 Impact Dynamics on Micropatterned Surfaces 342 10.5 Electrically Controlled Wettability Switching on Superhydrophobic Surfaces 344 10.5.1 Reversible Control of Wettability Using Electrostatic Methods 344 10.5.2 Electrowetting on Superhydrophobic Surfaces 345 10.5.3 Novel Strategies for Reversible Electrowetting on Rough Surfaces 348 10.6 Electrochemically Controlled Wetting of Superhydrophobic Surfaces 350 10.6.1 Polarity-Dependent Wetting of Nanotube Membranes 350 10.6.2 Mechanism of Polarity-Dependent Wetting and Transport 352 10.6.3 Potential Applications of Electrochemically Controlled Wetting and Transport 354 10.7 Summary and Future Perspectives 356 10.7.1 Future Perspectives 357 Acknowledgments 357 References 358 11 Imaging of Thin Films, and Its Application in the Life Sciences 363 Silvia Mittler 11.1 Introduction 363 11.2 Thin Film Preparation Methods 364 11.2.1 Dip-Coating 364 11.2.2 Spin-Coating 364 11.2.2 Langmuir–Blodgett (LB) Films 364 11.2.4 Self-Assembled Monolayers 366 11.2.5 Layer-by-Layer Assembly 366 11.2.6 Polymer Brushes: The “Grafting-From” Approach 367 11.3 Structuring: The Micro- and Nanostructuring of Thin Films 368 11.3.1 Photolithography 368 11.3.2 Ion Lithography and FIB Lithography 369 11.3.3 Electron Lithography 369 11.3.4 Micro-Contact Printing and Nanoimprinting (NIL) 369 11.3.5 Near-Field Scanning Methods 370 11.3.6 Other Methods 371 11.4 Imaging Technologies 371 11.4.1 The Concept of Total Internal Refl ection 371 11.4.2 The Concept of Waveguiding 372 11.4.3 Brewster Angle Microscopy (BAM) 373 Contents XI 11.4.4 Resonant Evanescent Methods 375 11.4.4.1 Surface Plasmon Resonance Microscopy 375 11.4.4.2 Waveguide Resonance Microscopy 376 11.4.4.3 Surface Plasmon Enhanced Fluorescence Microscopy 378 11.4.4.4 Waveguide Resonance Microscopy with Electro-Optical Response 379 11.4.5 Nonresonant Evanescent Methods 379 11.4.5.1 Total Internal Refl ection Fluorescence (TIRF) Microscopy 379 11.4.5.2 Waveguide Scattering Microscopy 380 11.4.5.3 Waveguide Evanescent Field Fluorescence Microscopy (WEFFM) 381 11.4.5.4 Confocal Raman Microscopy and One- and Two-Photon Fluorescence Confocal Microscopy 382 11.5 Application of Thin Films in the Life Sciences 383 11.5.1 Sensors 384 11.5.2 Surface Functionalization for Biocompatibility 384 11.5.3 Drug Delivery 385 11.5.4 Bioreactors 386 11.5.5 Cell-Surface Mimicking 387 11.6 Summary 389 References 390 12 Structural Characterization Techniques of Molecular Aggregates, Polymer, and Nanoparticle Films 397 Takeshi Hasegawa 12.1 Introduction 397 12.2 Characterization of Ultrathin Films of Soft Materials 398 12.2.1 X-Ray Diffraction Analysis 398 12.2.2 Infrared Transmission and Refl ection Spectroscopy 402 12.2.3 Multiple-Angle Incidence Resolution Spectrometry (MAIRS) 406 12.2.3.1 Theoretical Background of MAIRS 406 12.2.3.2 Molecular Orientation Analysis in Polymer Thin Films by IR-MAIRS 408 12.2.3.3 Analysis of Metal Thin Films 411 References 415 Index 419 1 1 Polymer Thin Films for Biomedical Applications Venkat K. Vendra , Lin Wu , and Sitaraman Krishnan 1.1 Introduction Modern medicine uses a variety of synthetic materials and devices to treat medical conditions and diseases. Biomedical devices such as coronary stents, vascular grafts, heart valves, blood bags, blood oxygenators, renal dialyzers, catheters, hip prostheses, knee prostheses, intraocular lenses, contact lenses, cochlear implants, and dental implants have defi nitely played an important role in transforming lives and improving the quality of living. Advances in protein -b ased drugs, gene therapy, targeted drug delivery, and tissue engineering have the potential to revolutionize contemporary medicine. Artifi cial skins to treat burn victims, artifi cial pancreas for people with diabetes, and cardiac patches to regenerate cardiac muscle damaged by a heart attack, no longer seem far - fetched, because of developments in tissue engineering. Thus, a wide range of synthetic materials are used to evaluate, treat, augment or replace any tissue, organ or function of the body. “ Biomaterial ” is a term used to categorize such materials and devices that directly “ interact ” with human tissues and organs [1] . The interactions may involve, for example, platelet aggregation and blood coagulation in the case of blood- c ontacting devices, immune response and foreign body reactions around biomaterials or devices implanted in the body, or more desirably, structural and functional connection between the implant and the host tissue (this is termed osseointegration in the case of dental and orthopedic implants). Biomaterials interact with biological systems through their surfaces. It is, there- fore, vitally important to control the surface properties of a biomaterial so that it integrates well with host tissues – that is, to make the material “ biocompatible ” [2] . Organic thin fi lms and coatings, particularly those of polymers, are very attractive as biomaterial coatings because they offer great versatility in the chemical groups that can be incorporated at the surface (to control tissue – biomaterial interactions); the coatings also have mechanical properties that are similar to soft biological tissues. The relative ease of processing is another reason for the extensive interest in organic thin fi lms. Biomaterial surfaces can be coated with polymers using Nanomaterials for the Life Sciences Vol.5: Nanostructured Thin Films and Surfaces. Edited by Challa S. S. R. Kumar Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32155-1