Single-Chain Polymer Nanoparticles: Synthesis, Characterization, Simulations, and Applications

This first book on this important and emerging topic presents an overview of the very latest results obtained in single-chain polymer nanoparticles obtained by folding synthetic single polymer chains, painting a complete picture from synthesis via characterization to everyday applications. The initial chapters describe the synthetics methods as well as the molecular simulation of these nanoparticles, while subsequent chapters discuss the analytical techniques that are applied to characterize them, including size and structural characterization as well as scattering techniques. The final chapters are then devoted to the practical applications in nanomedicine, sensing, catalysis and several other uses, concluding with a look at the future for such nanoparticles. Essential reading for polymer and materials scientists, materials engineers, biochemists as well as environmental chemists.

Table of Contents:
1 SyntheticMethods Toward Single-Chain Polymer Nanoparticles 1 Ozcan Altintas, Tobias S. Fischer, and Christopher Barner-Kowollik 1.1 Introduction 1 1.2 Single-Chain Rings via Irreversible and Reversible Bonds 2 1.3 Single-Chain Nanoparticles via Irreversible Bonds 8 1.4 Single-Chain Nanoparticles via Supramolecular Chemistry 17 1.5 Single-Chain Nanoparticles Based on Dynamic Covalent Chemistry 32 1.6 Conclusions and Outlook 33 Acknowledgments 34 References 34 2 Computer Simulations of Single-Chain Nanoparticles 47 Angel J.Moreno and Federica Lo Verso 2.1 Computer Simulations in Soft Matter Science 47 2.2 Simulation of Single-Chain Nanoparticles: Antecedents 49 2.3 A Bead–SpringModel for Single-Chain Nanoparticles 50 2.4 Conventional Routes in Good Solvent: Sparse Single-Chain Nanoparticles 53 2.4.1 The Simple Case: SCNPs from Homofunctional Precursors 54 2.4.2 SCNPs Synthesis via Orthogonal and Multi-orthogonal Protocols 57 2.5 Routes to Globular Single-Chain Nanoparticles 61 2.5.1 Bonding Mediated by Long Linkers 63 2.5.2 Solvent-Assisted Routes 64 2.6 Sparse SCNPs: Analogies with Intrinsically Disordered Proteins 70 2.7 Globular SCNPs: A New Class of Soft Colloids 75 2.8 Conclusions and Outlook 79 2.9 SCNPs as Nanofillers in All-Polymer Nanocomposites 80 2.10 Nonlinear Rheology of SCNPs 81 2.11 SCNPs under Pulling Forces 81 Acknowledgments 82 References 82 3 Characterization of Single-Chain Polymer Nanoparticles: Analytical Techniques 91 Ashley M. Hanlon, Kyle J. Rodriguez, Ruiwen Chen, Elizabeth Bright, and Erik B. Berda 3.1 Introduction 91 3.2 Single-Chain Polymer Nanoparticle Characterization via Size Exclusion Chromatography (SEC) 92 3.2.1 Standard Calibration SEC 92 3.2.2 Measuring Single-Chain Polymer Nanoparticle Formation via SEC-MALS 98 3.2.3 Measuring Single-Chain Polymer Nanoparticle Formation via SEC and Viscometry 100 3.3 Spectroscopic Characterization of Single-Chain Polymer Nanoparticles 102 3.3.1 Single-Chain Polymer Nanoparticle Characterization via Standard 1D 1HNMR 103 3.3.2 Single-Chain Polymer Nanoparticle Characterization via Other Nuclei 1D NMR 103 3.3.3 Single-Chain Polymer Nanoparticle Structural and Conformational Characterization via NMR 104 3.3.4 Single-Chain Polymer Nanoparticle Characterization via IR, UV–vis, CD, and Fluorescence Spectroscopy 110 3.4 Characterization of Single-Chain Polymer Nanoparticle Morphology 112 3.4.1 Morphological Characterization via TEM 112 3.4.2 Morphological Characterization via AFM 114 3.4.3 Morphological Characterization via Scattering 120 3.5 Conclusions and Outlook 122 References 123 4 Structure and Dynamics of Systems Based on Single-Chain Polymer Nano-Particles Investigated by Scattering Techniques 129 Arantxa Arbe and Juan Colmenero 4.1 Introduction 129 4.2 Scattering Experiments 130 4.3 Sources and Instrumentation 136 4.3.1 Sources 136 4.3.2 Diffraction 136 4.3.3 Quasielastic Neutron Scattering 138 4.4 Application of Scattering Techniques to Polymeric Systems 140 4.4.1 Polymer Melts 140 4.4.2 Polymer Solutions 146 4.5 SCNPs in Dilute Solution 148 4.5.1 How Globular Are SCNPs in Good Solvent? 149 4.5.2 Chain Dynamics 152 4.6 SCNPs in Bulk 158 4.7 All-Polymer Nano-Composites: SCNPs Dispersed in a Linear Polymer Matrix 159 4.7.1 Interpenetration of the components 160 4.7.2 Dynamic Asymmetry 162 4.7.3 Selecting Component Contributions by Deuterium Labeling 163 4.7.4 Dynamics of SCNPs Observed by QENS 165 4.7.5 Linear Polymer Matrix Dynamics 165 4.8 SCNPs as Confining Medium of Linear Chains 172 4.9 Conclusions 173 Acknowledgments 174 References 174 5 Dynamically Folded Single-Chain Polymeric Nanoparticles 183 Yiliu Liu and Anja R.A. Palmans 5.1 Introduction 183 5.2 Single-Chain Polymeric Nanoparticles versus Conventional Nanoparticles 184 5.3 Preparation of Dynamically Folded Single-Chain Polymeric Nanoparticles 186 5.4 Characterization of Dynamically Folded Single-Chain Polymer Nanoparticles 200 5.5 Conclusions and Future Outlook 207 References 209 6 Metal Containing Single-Chain Nanoparticles 217 Inbal Berkovich, Victoria Kobernik, Stefano Guidone and N. Gabriel Lemcoff 6.1 Introduction 217 6.2 Palladium 218 6.3 Iron 222 6.4 Copper 228 6.5 Other Metals 239 6.5.1 Rhodium, Iridium, and Nickel 239 6.5.2 Ruthenium 242 6.5.3 Zinc 246 6.5.4 Gold 247 6.5.5 Gadolinium 250 6.5.6 Gallium 251 6.6 Conclusions and Outlook 253 References 253 7 Colloidal Unimolecular Polymer Particles: CUP 259 Michael R. Van De Mark, Ashish Zore, Peng Geng, and Fei Zheng 7.1 Introduction 259 7.2 Synthesis 260 7.2.1 Monomers and Ratio, MolecularWeight, Glass Transition, Cup Size, and Functionality 264 7.2.2 Reduction and CUP Formation 264 7.2.3 Collapse Point 265 7.2.4 CUP Size and Distribution Correlation to MolecularWeight 266 7.3 Formation of CUPs Particles 267 7.3.1 Entropy Effect/Soap Theory 267 7.3.2 Hydrophilic/Lipophilic Balance (HLB) 269 7.3.3 Flory–Huggins Theory 270 7.4 Conformation of the CUP Particles 271 7.5 Electrokinetic Behavior in CUPs 271 7.5.1 Zeta Potential, Debye–Hückel Parameter and Electrophoretic Mobility 272 7.5.2 Determining the Effective Nuclear Charge 272 7.5.2.1 Nernst–EinsteinModel 272 7.5.2.2 Hessingers Model 273 7.5.2.3 Charge Renormalization 273 7.5.3 Electrokinetic Behavior in COO− CUPs 273 7.6 Electroviscous Effect in CUPs 274 7.6.1 Electroviscous Effect:Theory 275 7.6.1.1 Primary Electroviscous Effect 275 7.6.1.2 Secondary Electroviscous Effect 276 7.6.1.3 Tertiary Electroviscous Effect 277 7.6.2 Intrinsic Viscosity Determination 277 7.6.3 SurfaceWater Determination 277 7.6.4 Electroviscous Effect in CUPs 278 7.6.4.1 Electroviscous Effect in COO− CUPs 278 7.6.4.2 Electroviscous Effect in SO−3 CUPs 278 7.6.4.3 Electroviscous Effect in QUAT CUPs 279 7.6.5 Effect of Salts on Rheology 279 7.7 Gel Point Behavior 280 7.7.1 Packing in CUPs 280 7.7.2 Gel Point Study 281 7.7.2.1 Determination of Gel Point 281 7.7.2.2 Viscosity Measurements 281 7.7.2.3 Maximum Packing Volume Fraction, Density, andThickness of SurfaceWater 282 7.7.3 Comparison with Commercial Resins like Latex and Polyurethane Dispersions 284 7.8 Surface Tension Behavior 285 7.8.1 Equilibrium Surface Tension Behavior 286 7.8.1.1 Effect of Concentration on Equilibrium Surface Tension 286 7.8.1.2 Effect of MolecularWeight on Equilibrium Surface Tension 287 7.8.1.3 Effect of Surface Active Groups on Equilibrium Surface Tension 288 7.8.2 Dynamic Surface Tension Behavior 288 7.8.2.1 Effect of MolecularWeight on Kinetic Relaxation Time 289 7.8.2.2 Effect of Concentration on Kinetic Relaxation Time 290 7.8.2.3 Effect of MolecularWeight on Dynamic Surface Tension 290 7.8.2.4 Effect of Concentration on Dynamic Surface Tension 290 7.9 Cup SurfaceWater 291 7.9.1 Electroviscous Effect and Gel Point 291 7.9.2 Differential Scanning Calorimetry 291 7.9.3 NMR Relaxation Study 293 7.9.3.1 Proton NMR Spin–Lattice Relaxation Time Constant versus CUP Concentration 293 7.9.3.2 Proton NMR Spin–Lattice Relaxation Time Constant versus Temperature 294 7.9.3.3 Calculation of BoundWater Amount 295 7.10 Study of Core Environment of CUPs 297 7.10.1 F19 NMR T2 Relaxation Experiment 297 7.11 Applications: Use of CUPs in Coatings 298 7.11.1 Acrylic CUP Coating Lacquers 298 7.11.2 Aziridine-Cured Acrylic CUPs Resin 299 7.11.3 Use of CUPs with Melamine Resin Cross-Linking 300 7.11.4 Use of Sulfonate CUPs as Catalyst for Melamine Cure Systems 301 7.11.5 Epoxy 302 7.11.6 Use of CUPs as Additive for Freeze–Thaw Stability andWet Edge Retention 305 References 306 8 Single-Chain Nanoparticles via Self-Folding Amphiphilic Copolymers in Water 313 Takaya Terashima andMitsuo Sawamoto 8.1 Introduction 313 8.2 Single-Chain Folding Amphiphilic Random Copolymers 315 8.2.1 Hydrophobic Alkyl Pendants 316 8.2.2 Hydrophobic/Hydrogen-Bonding Pendants 321 8.2.3 Fluorous Perfluorinated Pendants 326 8.3 Precision Self-Assembly and Self-Sorting of Amphiphilic Random Copolymers 329 8.4 Single-chain crosslinked star polymers 332 8.5 Conclusions and Future Directions 335 References 335 9 Applications of Single-Chain Polymer Nanoparticles 341 Jon Rubio-Cervilla and Edurne González and José A. Pomposo 9.1 Introduction 341 9.1.1 Single-Chain Soft Nano-Objects 341 9.1.2 Reversible Versus Irreversible Single-Chain Polymer Nanoparticles 345 9.1.3 Main Applications of Single-Chain Polymer Nanoparticles 346 9.2 Nanomedicine 347 9.2.1 Controlled Drug Delivery Systems 349 9.2.1.1 Single-Chain Polymer Nanoparticles for Controlled Delivery of Chiral Amino Acid Derivatives 349 9.2.1.2 Single-Chain Polymer Nanoparticles for Controlled Delivery of Peptides 350 9.2.1.3 Single-Chain Polymer Nanoparticles for Controlled Delivery of Vitamins 351 9.2.1.4 Single-Chain Polymer Nanoparticles for Controlled Delivery of Drugs 353 9.2.2 Image Contrast Agents 355 9.2.2.1 Single-Chain Polymer Nanoparticles for Magnetic Resonance Imaging 355 9.2.2.2 Single-Chain Polymer Nanoparticles for Single Photon Emission Computerized Tomography 356 9.2.2.3 Single-Chain Polymer Nanoparticles for Fluorescence Imaging 356 9.3 Catalysis 360 9.3.1 Single-Chain Polymer Nanoparticles as Nanoreactors for the Synthesis of Chemical Compounds 361 9.3.2 Single-Chain Polymer Nanoparticles as Nanoreactors for the Synthesis of Polymers 365 9.3.2.1 Ring-Opening Polymerization 365 9.3.2.2 Controlled Radical Polymerization 366 9.3.3 Single-Chain Polymer Nanoparticles as Nanoreactors for the Synthesis of Nanomaterials 367 9.3.3.1 Gold Nanoparticles 367 9.3.3.2 Quantum Dots 367 9.3.3.3 Carbon Nanodots 368 9.4 Sensing 369 9.4.1 Single-Chain Polymer Nanoparticles as Sensors of Metal Ions 369 9.4.2 Single-Chain Polymer Nanoparticles as Sensors of Proteins 369 9.5 Other Uses 371 9.5.1 Porogens for Microelectronic Applications 371 9.5.2 Functional Nanoparticles for Bioscience 372 9.5.3 Reversible Hydrogels 373 9.5.4 Supramolecular Films 373 9.5.5 Rheology Modifiers 374 9.5.6 All-Polymer Nanocomposites 374 9.5.7 Surfactants 375 9.6 Conclusions and Outlook 376 Acknowledgments 378 References 378 Index 389

About the Author :
Jose A. Pomposo is IKERBASQUE Research Professor at the Materials Physics Department of the University of the Basque Country - UPV/EHU. He is in charge of the Chemistry Laboratory oriented to Polymer Synthesis of the Polymers & Soft Matter Group. He received his Ph.D. from the University of the Basque Country in 1994. He spent 12 years as Head of the New Materials Department in a Technological Research Center, and 1 year at the Donostia International Physics Center - DIPC. He has contributed to more than 130 scientific publications and 9 international patents. His research interests include the synthesis of uniform soft nano-objects, research on the structure, dynamics & self-assembly behaviour of complex single-chain nano-objects, and the construction of hybrid organic nanostructures.