Hairy Nanoparticles

Dr. Zhiqun Lin is currently Professor of Chemical and Biomolecular Engineering at the National University of Singapore (NUS). He received his PhD in Polymer Science and Engineering from the University of Massachusetts, Amherst in 2002. Yijiang Liu is an Associate Professor in the College of Chemistry at the Xiangtan University. She received her PhD from the Institute of Chemistry, Chinese Academy of Sciences in 2015.

• Preface xiii1 Synthesis of Hairy Nanoparticles 1Zongyu Wang, Jiajun Yan, Michael R. Bockstaller, and Krzysztof Matyjaszewski1.1 Introduction to Grafting Chemistry 11.2 Surface Functionalization of Nanoparticles 21.2.1 Surface Modification by Chemical Treatment 21.2.2 Surface Modification by Plasma Treatment 81.2.3 Synthesis of Functionalized Nanoparticles Through Initiator-Containing Precursors 81.3 Synthesis of Hairy Nanoparticles 91.3.1 Surface-Initiated Polymerization/The “Grafting-from” Approach 91.3.1.1 SI-Free Radical Polymerization 101.3.1.2 Si-atrp 101.3.1.3 Si-raft 171.3.1.4 Other Polymerization Techniques 191.3.2 The “Grafting-onto” Approach 211.3.2.1 Conventional “Grafting-onto” Approach 211.3.2.2 Ligand Exchange 231.3.3 Template Synthesis 241.3.3.1 Block Copolymer and Its Derivative Templates 241.3.3.2 Star/Bottlebrush Polymer Templates 251.4 The Role of “Architecture” in Hairy Nanoparticles 251.4.1 Conformation of Hairy Nanoparticles 261.4.2 Bimodal Hairy Nanoparticles 311.5 Conclusion 32Acknowledgment 34References 342 Hairy Nanoparticles via Self-assembled Linear Block Copolymers 49Zhen Zhang, Yi Shi, and Yongming Chen2.1 Introduction 492.2 Hairy NPs via Bulk Microphase Separation of Block Copolymers 502.2.1 Bulk Microphase Separation of Diblock Copolymers 502.2.1.1 Theoretical Research 512.2.1.2 Experimental Study 522.2.1.3 Effect Factors 532.2.2 Bulk Microphase Separation of Triblock Copolymers 542.2.3 Preparation of Hairy NPs with Different Shapes 552.2.3.1 Diblock Copolymers with PTEPM or PGMA Components 562.2.3.2 Diblock Copolymers Containing PS 562.2.3.3 Triblock Copolymer System with PS Components 592.3 Hairy NPs via the Self-assembly of Block Copolymer in Solution 612.3.1 Morphology of Block Copolymers Assembly 622.3.1.1 Spherical Micelles 622.3.1.2 Rod-Like Micelles 632.3.1.3 Bilayer Structure 632.3.1.4 New Morphologies 642.3.2 Preparation of Hairy Copolymer NPs 652.3.3 Major Factors Influencing the Morphology of Hairy NPs 652.3.3.1 Block Copolymer Composition 652.3.3.2 Block Copolymer Concentration 662.3.3.3 The Nature of the Solvent 662.3.3.4 Additives 672.3.3.5 Other Factors 682.4 Summary 69References 693 Hairy Nanoparticles via Unimolecular Block Copolymer Nanoreactors 73Wenjie Zhang and Xinchang Pang3.1 Background 733.2 Synthesis and Properties of Block Copolymer Unimolecular Micelles 753.2.1 Properties of Unimolecular Block Copolymer Micelles 753.2.2 Synthesis and Features of Star-Liked Block Copolymers 773.2.2.1 Synthesis of Star-Liked Block Copolymers via Core-First Method 773.2.2.2 Synthesis of Star-Liked Block Copolymers via Arm-First Method 833.2.3 Synthesis of Bottle Brush-Liked Block Copolymer 843.3 Synthesis of Monodispersed Nanoparticles via Block Copolymer Unimolecular Micelles Nanoreactors 883.3.1 Star-Like Block Copolymers as Unimolecular Nanoreactors 883.3.1.1 Plain Nanoparticles 883.3.1.2 Core@Shell Nanoparticles 943.3.1.3 Hollow Nanoparticles 973.3.1.4 Nanoring 993.3.1.5 Colloidal Nanoparticles Assemblies 1023.3.2 Cylindrical Polymer Brushes as Unimolecular Nanoreactors 1043.4 Application of Polymer-Capped Nanoparticles 1113.4.1 Solar Energy Conversion 1123.4.2 Light-Emitting Diodes 1133.4.3 Lithium-Ion Batteries 1143.4.4 Catalysis 1153.5 Conclusions and Perspectives 1173.5.1 Conclusion 1173.5.2 Perspectives 117References 1194 Environmentally Responsive Hairy Inorganic Particles 123Caleb A. Bohannon, Ning Wang, and Bin Zhao4.1 Introduction 1234.2 Environmentally Responsive Well-defined Binary Mixed Homopolymer Brush-grafted Silica Particles 1264.2.1 Introduction to Mixed Polymer Brushes 1264.2.2 Mixed Polymer Brushes Grafted on Particles 1294.2.3 Synthesis of Well-defined Binary Mixed Homopolymer Brushes on Silica Particles 1304.2.4 Responsive Properties of Binary Mixed Homopolymer Brush-grafted Silica Particles 1344.3 Thermoresponsive Polymer Brush-grafted Silica Particles 1414.3.1 Synthesis and Thermally Induced LCST Transition of Thermoresponsive Polymer Brushes Grafted on Silica Particles 1414.3.2 Thermally Induced Phase Transfer of Thermoresponsive Hairy Particles Between Two Immiscible Liquid Phases 1444.3.2.1 Thermally Induced Phase Transfer of Thermoresponsive Hairy Particles Between Water and Immiscible Organic Solvents 1444.3.2.2 Thermally induced Phase Transfer of Thermoresponsive Hairy Particles Between Water and a Hydrophobic Ionic Liquid 1464.3.3 Thermoreversible Gelation of Thermoresponsive Diblock Copolymer Brush-grafted Silica Nanoparticles in Water 1504.3.4 Thermoresponsive Polymer Brush-grafted Nanoparticles for Enhancing Gelation of Thermoresponsive Linear ABC Triblock Copolymers in Water 1564.4 Summary and Outlook 160Acknowledgements 161References 1615 Self-Assembly of Hairy Nanoparticles with Polymeric Grafts 167Xiaoxue Shen, Huibin He, and Zhihong Nie5.1 Introduction 1675.2 Self-Assembly of PGNPs into Colloidal Molecules 1685.2.1 Precisely Defined Assembly of Patchy NPs 1685.2.1.1 Isotropic NPs 1695.2.1.2 Anisotropic NPs 1715.2.2 Polymer-Guided Assembly of NPs 1725.3 Self-Assembly of PGNPs Into One-Dimensional (1-D) Structures 1755.3.1 Self-Assembly of PGNPs in Solution Guided by Various Molecular Interactions 1765.3.1.1 Self-Assembly Driven by Neutralization Reaction 1765.3.1.2 Self-Assembly Driven by Hydrophobic Interaction 1785.3.1.3 Self-Assembly Driven by Dipolar Interaction 1805.3.2 Templated Self-Assembly of PGNPs into 1-D Structures 1825.3.2.1 Hard Template-Assisted Assembly of PGNPs 1825.3.2.2 Self-Assembly of PGNPs Assisted by Soft Templates 1845.3.3 The Self-Assembly of 1-D Structures in Polymer Films 1875.4 Self-Assembly of PGNPs into 2-D Structures 1905.4.1 Templated Self-Assembly of PGNPs into 2-D Structures 1905.4.1.1 Self-Assembly Using BCPs as Templates 1905.4.1.2 Hard Template-Assisted Self-Assembly 1935.4.2 Interfacial Assembly 1935.4.3 2-D Assemblies Within Thin Film 1975.4.3.1 PGNPs/Homopolymer System 1975.4.3.2 Self-Assembly of Single-Component Neat PGNPs 1995.4.3.3 Self-Assembly of Binary PGNPs Blends 2015.5 Self-Assembly of PGNPs into 3-D Structures 2025.5.1 Self-Assembly of PGNPs into Clusters 2025.5.2 Self-Assembly of PGNPs into Vesicles 2065.5.2.1 Self-Assembly of Hydrophilic Homopolymer-Grafted NPs 2065.5.2.2 Self-Assembly of Mixed Homopolymer-Grafted NPs (M-PGNPs) 2065.5.2.3 Self-Assembly of BCP-Grafted NPs (B-PGNPs) 2095.5.2.4 Co-Assembly of Binary B-PGNPs or B-PGNPs/BCPs 2105.5.3 Self-Assembly of PGNPs into 3-D Superlattices and Crystals 2125.5.3.1 Superlattices and Crystals Assembled in Solution 2125.5.3.2 Binary Superlattice Assembled at Interfaces 2145.6 Representative Applications of Assembled PGNPs 2155.6.1 Biological Applications: Imaging, Therapy, and Drug Delivery 2155.6.1.1 Assemblies of Plasmonic PGNPs 2165.6.1.2 Assemblies of Magnetic PGNPs 2165.6.1.3 Assemblies of Plasmonic-Magnetic PGNPs 2175.6.2 Dielectric Materials 2185.7 Summary and Outlook 219References 2206 Interfacial Property of Hairy Nanoparticles 227Yilan Ye and Zhenzhong Yang6.1 Introduction 2276.2 Hairy NPs as Interfacial Building Blocks 2286.2.1 Conformation of Grafted Polymers in Good Solvents 2286.2.2 Patchy and Janus Geometry in Selective Solvents 2306.2.3 Interfacial Activity as Colloids 2336.3 Hairy NPs Assembly at Various Interfaces 2356.3.1 Dispersion in Polymer Nanocomposites 2356.3.2 Anisotropic Assembly 2376.3.3 Liquid–Liquid Interfaces 2406.3.4 Air–Solid Surfaces 2436.3.5 Air–Liquid Surfaces 2446.4 Interfacial Entropy 2466.5 Interfacial Jamming 2486.5.1 Electrostatic Assembly 2486.5.2 Host–Guest Molecular Recognition 2516.6 Single-Chain NPs at Interfaces 2516.6.1 Efficient Synthesis 2516.6.1.1 Electrostatic-Mediated Intramolecular Crosslinking Toward Large-Scale Synthesis of SCNPs 2526.6.1.2 Grafting Single-Chain at NPs 2556.6.2 Interfacial Applications 256References 2587 Hairy Hollow Nanoparticles 261Huiqi Zhang7.1 Introduction 2617.2 Overview of the Progress in the Design and Synthesis of Hairy Hollow NPs 2627.2.1 Synthetic Strategies for Hairy Hollow Polymer NPs 2627.2.1.1 Sacrificial Template Method 2637.2.1.2 Self-Assembly (of Block Copolymers) Method 2827.2.1.3 Single-Molecule Templating (of Core–Shell Bottlebrush Polymers) Method 2887.2.2 Synthetic Strategies for Hairy Hollow Inorganic NPs 2937.2.2.1 Direct Grafting of Polymer Brushes onto Hollow Inorganic NPs 2937.2.2.2 Sacrificial Template Strategy Combined with Sol–Gel Chemistry and Polymer Brush-Grafting Methods 2967.2.3 Synthetic Strategies for Hairy Hollow Organic/Inorganic Hybrid NPs 3027.2.3.1 Direct Deposition of Polymer Layers onto Hollow Inorganic NPs by SI-Polymerizations 3027.2.3.2 Self-Assembly Method 3027.2.3.3 Single-Molecule Templating Method 3047.2.3.4 Sacrificial Template Method Combined with Polymer Brush Nanoreactors 3057.3 Conclusions and Perspectives 306Acknowledgment 308References 3088 Self-Assembly of Binary Mixed Homopolymer Brush-Grafted Silica Nanoparticles 313Bin Zhao, Ping Tang, Phoebe L. Stewart, Rong-Ming Ho, Christopher Y. Li, and Lei Zhu8.1 Introduction 3138.2 Computer Simulations of the Self-Assembled Morphology of MBNPs 3158.3 Self-Assembled Morphologies of Well-Defined Binary Mixed Homopolymer Brushes Grafted on Silica NPs 3188.3.1 Synthesis of Well-Defined Binary Mixed Homopolymer Brush-Grafted Silica NPs 3188.3.2 Lateral Microphase Separation of Nearly Symmetric PtBA/PS MBNPs 3198.3.3 Effect of Chain Length Disparity on the Self-Assembled Morphology of PtBA/PS MBNPs 3208.3.4 Effect of Overall Grafting Density on Morphology of PtBA/PS MBNPs 3248.3.5 Effect of Molecular Weight on Morphology of Symmetric MBNPs 3278.3.6 Effect of Core Particle Size on Morphology of PtBA/PS MBNPs 3328.3.7 3D Morphologies of PtBA/PS MBNPs by Cryo-TEM and Electron Tomography 3358.4 Self-Assembled Morphology in Solvents and Homopolymer Matrices 3398.4.1 Self-Assembly of MBNPs in Good and Selective Solvents 3398.4.2 Self-Assembly of MBNPs in Homopolymer Matrices with Different Molecular Weights 3418.5 Conclusions and Future Work 346Acknowledgment 346References 3479 Hairy Plasmonic Nanoparticles 351Christian Rossner, Tobias A.F. König, and Andreas Fery9.1 Introduction 3519.2 Plasmonic Properties of Isolated NPs and Energy Transfer to Adjacent Hairy Environment 3549.2.1 Plasmonic Principles of Hairy NPs 3549.2.2 Energy Transfer to Adjacent Hairy Environment 3589.2.2.1 Hairy NPs for Photothermal Heating 3589.2.2.2 Hairy NPs Conjugated with Photoactive Entities 3609.2.2.3 Hairy NPs Conjugated with Acceptors 3619.3 Plasmonic Coupling Scenarios of Hairy Plasmonic NPs 3629.3.1 Supercolloidal Structures in Solution 3629.3.2 Hairy NPs Linked to Surface and Self-assembly 3669.4 Summary and Outlook Discussions 368Acknowledgments 370References 37010 Hairy Metal Nanoparticles for Catalysis: Polymer Ligand-Mediated Catalysis 375Zichao Wei and Jie He10.1 Nanocatalysis Mediated by Surface Ligands 37510.1.1 Surface Ligands as an Important Component for Nanocatalysis 37510.1.2 Polymers as Better Ligands for NPs 37710.2 Catalysis Mediated by PGNPs with Thiol-Terminated Polymers 38010.3 Catalysis Mediated by PGNPs with NHC-Terminated Polymers 38710.4 Other PGNP Nanocatalysts 39310.5 Conclusion and Outlook 396References 39711 Hairy Inorganic Nanoparticles for Oil Lubrication 401Michael T. Kelly and Bin Zhao11.1 Introduction 40111.1.1 Oil Lubrication 40111.1.2 Nanoparticles as Oil Lubricant Additives for Friction and Wear Reduction 40211.1.3 Polymer Brush-Grafted Nanoparticles: Definition and Synthesis 40411.2 Oil-Soluble Poly(lauryl methacrylate) Brush-Grafted Metal Oxide NPs as Lubricant Additives 40611.2.1 Synthesis, Dispersibility, and Stability in PAO of Poly(lauryl methacrylate) Brush-Grafted Silica and Titania NPs 40611.2.2 Lubrication Properties of Poly(lauryl methacrylate) Brush-Grafted Silica and Titania NPs in PAO 41011.3 Effects of Alkyl Pendant Groups on Oil Dispersibility, Stability, and Lubrication Property of Poly(alkyl methacrylate) Brush-Grafted Silica Nanoparticles 41311.3.1 Synthesis of Poly(alkyl methacrylate) Brush-Grafted, 23-nm Silica NPs 41311.3.2 Dispersibility and Stability of 23-nm Silica NPs Grafted with Poly(alkyl methacrylate) Brushes with Various Pendant Groups in PAO- 4 41411.3.3 Effect of Alkyl Side Chains of Poly(alkyl methacrylate) Brushes on Lubrication Performance of 23-nm Hairy Silica NPs as Additives for Pao- 4 41611.4 Improved Lubrication Performance by Combining Oil-Soluble Hairy Silica Nanoparticles and an Ionic Liquid as Additives for PAO- 4 42011.4.1 Preparation of PAO-4 Lubricants with Various Amounts of PLMA Hairy Silica NPs and [P8888][DEHP] and Stability of Hairy Silica NPs in the Presence of [P8888][DEHP] 42111.4.2 Lubrication Performances of PAO-4 Lubricants with the Addition of HNP, IL, and HNP + IL at Various Mass Ratios 42211.4.3 SEM–EDS and XPS Analysis of Wear Scars Formed on Iron Flats from Tribological Tests 42411.5 Upper Critical Solution Temperature (UCST)-Type Thermoresponsive Poly(alkyl methacrylate)s in PAO-4 42611.5.1 Synthesis of Poly(alkyl methacrylate)s with Various Alkyl Pendant Groups by RAFT Polymerization and Their Thermoresponsive Properties in PAO-4 42811.5.2 UCST-Type Thermoresponsive ABA Triblock Copolymers as Gelators for Pao-4 42911.6 Summary 432Acknowledgments 433References 433Index 437