Polymer and Biopolymer Brushes

OMAR AZZARONI, PHD, is currently the head of the Soft Matter Laboratory of INIFTA. His research interests include new applications of polymer brushes, nanostructured hybrid interfaces, supra- and macromolecular materials science, and soft nanotechnology. IGAL SZLEIFER, PHD, is the Christina Enroth-Cugell Professor of Biomedical Engineering and Professor of Chemistry, Chemical and Biological Engineering and Medicine at Northwestern University. He is a fellow of the American Physical Society and of the American Institute of Medical and Biological Engineers.

• Volume 1Preface xxiList of Contributors xxiii1 Functionalization of Surfaces Using Polymer Brushes: An Overview of Techniques, Strategies, and Approaches 1Juan M. Giussi,M. Lorena Cortez,Waldemar A. Marmisoll´e, and Omar Azzaroni1.1 Introduction: Fundamental Notions and Concepts 11.2 Preparation of Polymer Brushes on Solid Substrates 41.3 Preparation of Polymer Brushes by the “Grafting-To” Method 51.4 Polymer Brushes by the “Grafting-From” Method 91.4.1 Surface-Initiated Atom Transfer Radical Polymerization 91.4.2 Surface-Initiated Reversible-Addition Fragmentation Chain Transfer Polymerization 101.4.3 Surface-Initiated Nitroxide-Mediated Polymerization 131.4.4 Surface-Initiated Photoiniferter-Mediated Polymerization 131.4.5 Surface-Initiated Living Ring-Opening Polymerization 151.4.6 Surface-Initiated Ring-Opening Metathesis Polymerization 171.4.7 Surface-Initiated Anionic Polymerization 181.5 Conclusions 20Acknowledgments 21References 212 Polymer Brushes by AtomTransfer Radical Polymerization 29Guojun Xie, Amir Khabibullin, Joanna Pietrasik, Jiajun Yan, and KrzysztofMatyjaszewski2.1 Structure of Brushes 292.2 Synthesis of Polymer Brushes 312.2.1 Grafting through 312.2.2 Grafting to 322.2.3 Grafting from 322.3 ATRP Fundamentals 332.4 Molecular Bottlebrushes by ATRP 382.4.1 Introduction 382.4.2 Star-Like Brushes 402.4.3 Blockwise Brushes 422.4.4 Brushes with Tunable Grafting Density 452.4.5 Brushes with Block Copolymer Side Chains 462.4.6 Functionalities and Properties of Brushes 502.5 ATRP and Flat Surfaces 552.5.1 Chemistry at Surface 552.5.2 Grafting Density 552.5.3 Architecture 562.5.4 Applications 572.6 ATRP and Nanoparticles 582.6.1 Chemistry 582.6.2 Architecture 592.6.3 Applications 612.7 ATRP and Concave Surfaces 632.8 ATRP and Templates 632.8.1 Templates from Networks 632.8.2 Templates from Brushes 642.9 Templates from Stars 652.10 Bio-Related Polymer Brushes 662.11 Stimuli-Responsive Polymer Brushes 742.11.1 Stimuli-Responsive Solutions 762.11.2 Stimuli-Responsive Surfaces 782.12 Conclusion 79Acknowledgments 80References 803 Polymer Brushes by Surface-Mediated RAFT Polymerization for Biological Functions 97Tuncer Caykara3.1 Introduction 973.2 Polymer Brushes via the Surface-Initiated RAFT Polymerization Process 993.3 Polymer Brushes via the Interface-Mediated RAFT Polymerization Process 1013.3.1 pH-Responsive Brushes 1023.3.2 Temperature-Responsive Brushes 1063.3.3 Polymer Brushes on Gold Surface 1103.3.4 Polymer Brushes on Nanoparticles 1143.3.5 Micropatterned Polymer Brushes 1153.4 Summary 117References 1194 Electro-Induced Copper-Catalyzed Surface Modification with Monolayer and Polymer Brush 123Bin Li and Feng Zhou4.1 Introduction 1234.2 “Electro-Click” Chemistry 1244.3 Electrochemically Induced Surface-Initiated Atom Transfer Radical Polymerization 1294.4 Possible Combination of eATRP and “e-Click” Chemistry on Surface 1364.5 Surface Functionality 1364.6 Summary 137Acknowledgments 138References 1385 Polymer Brushes on Flat and Curved Substrates:What Can be Learned fromMolecular Dynamics Simulations 141K. Binder, S.A. Egorov, and A.Milchev5.1 Introduction 1415.2 Molecular Dynamics Methods: A Short “Primer” 1445.3 The Standard Bead Spring Model for Polymer Chains 1485.4 Cylindrical and Spherical Polymer Brushes 1505.5 Interaction of Brushes with Free Chains 1525.6 Summary 153Acknowledgments 156References 1576 Modeling of Chemical Equilibria in Polymer and Polyelectrolyte Brushes 161Rikkert J. Nap,Mario Tagliazucchi, Estefania Gonzalez Solveyra, Chun-lai Ren, Mark J. Uline, and Igal Szleifer6.1 Introduction 1616.2 Theoretical Approach 1636.3 Applications of the Molecular Theory 1776.3.1 Acid–Base Equilibrium in Polyelectrolyte Brushes 1786.3.1.1 Effect of Salt Concentration and pH 1786.3.1.2 Effect of Polymer Density and Geometry 1846.3.2 Competition between Chemical Equilibria and Physical Interactions 1866.3.2.1 Brushes of Strong Polyelectrolytes 1866.3.2.2 Brushes ofWeak Polyelectrolytes: Self-Assembly in Charge-Regulating Systems 1896.3.2.3 Redox-Active Polyelectrolyte Brushes 1936.3.3 End-Tethered Single Stranded DNA in Aqueous Solutions 1956.3.4 Ligand–Receptor Binding and Protein Adsorption to Polymer Brushes 2016.3.5 Adsorption Equilibrium of Polymer Chains through Terminal Segments: Grafting-to Formation of Polymer Brushes 2076.4 Summary and Conclusion 212Acknowledgments 216References 2167 Brushes of Linear and Dendritically Branched Polyelectrolytes 223E. B. Zhulina, F. A. M. Leermakers, and O. V. Borisov7.1 Introduction 2237.2 Analytical SCF Theory of Brushes Formed by Linear and Branched Polyions 2247.2.1 Dendron Architecture and System Parameters 2257.2.2 Analytical SCF Formalism 2267.3 Planar Brush of PE Dendrons with an Arbitrary Architecture 2297.3.1 Asymptotic Dependences for Brush Thickness H 2317.4 Planar Brush of Star-Like Polyelectrolytes 2327.5 Threshold of Dendron Gaussian Elasticity 2347.6 Scaling-Type Diagrams of States for Brushes of Linear and Branched Polyions 2357.7 Numerical SF-SCF Model of Dendron Brush 2367.8 Conclusions 238References 2398 Vapor Swelling of Hydrophilic Polymer Brushes 243Casey J. Galvin and Jan Genzer8.1 Introduction 2438.2 Experimental 2458.2.1 General Methods 2458.2.2 Synthesis of Poly((2-dimethylamino)ethyl methacrylate) Brushes with a Gradient in Grafting Density 2458.2.3 Synthesis of Poly(2-(diethylamino)ethyl methacrylate) Brushes 2458.2.4 Chemical Modification of Poly((2-dimethylamino)ethyl methacrylate) Brushes 2468.2.5 Bulk Synthesis of PDMAEMA 2468.2.6 Preparation of Spuncast PDMAEMA Films 2468.2.7 Chemical Modification of Spuncast PDMAEMA Film 2478.2.8 Spectroscopic EllipsometryMeasurements under Controlled Humidity Conditions 2478.2.9 Spectroscopic EllipsometryMeasurements of Alcohol Exposure 2478.2.10 Fitting Spectroscopic Ellipsometry Data 2488.2.11 Infrared Variable Angle Spectroscopic Ellipsometry 2488.3 Results and Discussion 2488.3.1 Comparing Polymer Brush and Spuncast Polymer Film Swelling 2508.3.2 Influence of Side Chain Chemistry on Polymer Brush Vapor Swelling 2528.3.3 Influence of Solvent Vapor Chemistry on Polymer Brush Vapor Swelling 2568.3.4 Influence of Grafting Density on Polymer Brush Vapor Swelling 2598.4 Conclusion 2628.A.1 Appendix 2638.A.1.1 Mole Fraction Calculation 2638.A.1.2 Water Cluster Number Calculation 264Acknowledgments 265References 2659 Temperature Dependence of the Swelling and Surface Wettability of Dense Polymer Brushes 267Pengyu Zhuang, Ali Dirani, Karine Glinel, and AlainM. Jonas9.1 Introduction 2679.2 The Swelling Coefficient of a Polymer Brush Mirrors Its Volume Hydrophilicity 2699.3 The Cosine of the Contact Angle ofWater on aWater-Equilibrated Polymer Brush Defines Its Surface Hydrophilicity 2709.4 Case Study: Temperature-Dependent Surface hydrophilicity of Dense PNIPAM Brushes 2729.5 Case Study: Temperature-Dependent Swelling and Volume Hydrophilicity of Dense PNIPAMBrushes 2749.6 Thermoresponsive Poly(oligo(ethylene oxide)methacrylate) Copolymer Brushes: Versatile Functional Alternatives to PNIPAM 2779.7 Surface and Volume Hydrophilicity of Nonthermoresponsive Poly(oligo(ethylene oxide)methacrylate) Copolymer Brushes 2799.8 Conclusions 282Acknowledgments 283References 28310 Functional Biointerfaces Tailored by “Grafting-To”Brushes 287Eva Bittrich, Manfred Stamm, and Petra Uhlmann10.1 Introduction 28710.2 Part I: Polymer Brush Architectures 28810.2.1 Design of Physicochemical Interfaces by Polymer Brushes 28810.2.1.1 Stimuli-Responsive Homopolymer Brushes 28810.2.1.2 Combination of Responses Using Mixed Polymer Brushes 29010.2.1.3 Stimuli-Responsive Gradient Brushes 29310.2.2 Modification of Polymer Brushes by Click Chemistry 29310.2.2.1 Definition of Click Chemistry 29310.2.2.2 Modification of End Groups of Grafted PNIPAAm Chains 29510.2.3 Hybrid Brush Nanostructures 29710.2.3.1 Nanoparticles Immobilized at Polymer Brushes 29810.2.3.2 Sculptured Thin Films Grafted with Polymer Brushes 30010.3 Part II: Actuating Biomolecule Interactions with Surfaces 30310.3.1 Adsorption of Proteins to Polymer Brush Surfaces 30310.3.1.1 Calculation of the Adsorbed Amount of Protein from Ellipsometric Experiments 30510.3.1.2 Preventing Protein Adsorption 30610.3.1.3 Adsorption at Polyelectrolyte Brushes 31010.3.2 Polymer Brushes as Interfaces for Cell Adhesion and Interaction 31310.3.2.1 Cell Adhesion on Stimuli-Responsive Polymer Surfaces Based on PNIPAAm Brushes 31510.3.2.2 Growth Factors on Polymer Brushes 31810.4 Conclusion and Outlook 320Acknowledgments 321References 32111 Glycopolymer Brushes Presenting Sugars in Their Natural Form: Synthesis and Applications 333Kai Yu and Jayachandran N. Kizhakkedathu11.1 Introduction and Background 33311.2 Results and Discussion 33411.2.1 Synthesis of Glycopolymer Brushes 33411.2.1.1 Synthesis of N-Substituted Acrylamide Derivatives of Glycomonomers 33411.2.1.2 Synthesis and Characterization of Glycopolymer Brushes on Gold Chip and SiliconWafer 33411.2.1.3 Synthesis and Characterization of Glycopolymer Brushes on Polystyrene Particles 33511.2.1.4 Synthesis and Characterization of Glycopolymer Brushes with Variation in the Composition of Carbohydrate Residues on SPR Chip 33811.2.1.5 Preparation of Glycopolymer Brushes-Modified Particles with Different Grafting Density (Conformation) 33811.2.2 Applications of Glycopolymer Brushes 34111.2.2.1 Antithrombotic Surfaces Based on Glycopolymer Brushes 34111.2.2.2 Glycopolymer Brushes Based Carbohydrate Arrays to Modulate Multivalent Protein Binding on Surfaces 34511.2.2.3 Modulation of Innate Immune Response by the Conformation and Chemistry of Glycopolymer Brushes 35111.3 Conclusions 356Acknowledgments 357References 35712 Thermoresponsive Polymer Brushes for Thermally Modulated Cell Adhesion and Detachment 361Kenichi Nagase and Teruo Okano12.1 Introduction 36112.2 Thermoresponsive Polymer Hydrogel-Modified Surfaces for Cell Adhesion and Detachment 36212.3 Thermoresponsive Polymer Brushes Prepared Using ATRP 36312.4 Thermoresponsive Polymer Brushes Prepared by RAFT Polymerization 36812.5 Conclusions 372Acknowledgments 372References 372Volume 2Preface xxiList of Contributors xxiii13 Biomimetic Anchors for Antifouling Polymer Brush Coatings 377Dicky Pranantyo, Li Qun Xu, En-Tang Kang, Koon-Gee Neoh, and Serena Lay-Ming Teo13.1 Introduction to Biofouling Management 37713.2 Polymer Brushes for Surface Functionalization 37813.3 Biomimetic Anchors for Antifouling Polymer Brushes 37913.3.1 Mussel Adhesive-Inspired Dopamine Anchors 37913.3.1.1 Antifouling Polymer Brushes Prepared via the “Grafting-To” Approach on (poly)Dopamine Anchor 38313.3.1.2 Antifouling Polymer Brushes Prepared via the “Grafting-From” Approach on (poly)Dopamine Anchor 38613.3.1.3 Direct Grafting of Antifouling Polymer Brushes Containing Anchorable Dopamine-Derived Functionalities 38913.3.2 (Poly)phenolic Anchors for Antifouling Polymer Brushes 39113.3.3 Biomolecular Anchors for Antifouling Polymer Brushes 39313.4 Barnacle Cement as Anchor for Antifouling Polymer Brushes 39713.5 Conclusion and Outlooks 399References 40014 Protein Adsorption Process Based on Molecular Interactions at Well-Defined Polymer Brush Surfaces 405Sho Sakata, Yuuki Inoue, and Kazuhiko Ishihara14.1 Introduction 40514.2 Utility of Polymer Brush Layers as Highly Controllable Polymer Surfaces 40614.3 Performance of Polymer Brush Surfaces as Antifouling Biointerfaces 40814.4 Elucidation of Protein Adsorption Based on Molecular Interaction Forces 41214.5 Concluding Remarks 416References 41715 Are Lubricious Polymer Brushes Antifouling? Are Antifouling Polymer Brushes Lubricious? 421Edmondo M. Benetti and Nicholas D. Spencer15.1 Introduction 42115.2 Poly(ethylene glycol) Brushes 42215.3 Beyond Simple PEG Brushes 42415.4 Conclusion 429References 42916 Biofunctionalized Brush Surfaces for Biomolecular Sensing 433Shuaidi Zhang and Vladimir V. Tsukruk16.1 Introduction 43316.2 Biorecognition Units 43516.2.1 Antibodies 43516.2.2 Antibody Fragments 43516.2.3 Aptamers 43716.2.4 Peptide Aptamers 43816.2.5 Enzymes 43816.2.6 Peptide Nucleic Acid, Lectin, and Molecular Imprinted Polymers 43916.3 Immobilization Strategy 43916.3.1 Through Direct Covalent Linkage 44016.3.1.1 Thiolated Aptamers on Noble Metal 44016.3.1.2 General Activated Surface Chemistry 44216.3.1.3 Diels–Alder Cycloaddition 44416.3.1.4 Staudinger Ligation 44416.3.1.5 1,3-Dipolar Cycloaddition 44616.3.2 Through Affinity Tags 44716.3.2.1 Biotin–Avidin/Streptavidin Pairing 44716.3.2.2 NTA–Ni2+–Histidine Pairing 44816.3.2.3 Protein A/Protein G – Fc Pairing 44916.3.2.4 Oligonucleotide Hybridization 45016.4 Microstructure and Morphology of Biobrush Layers 45116.4.1 Grafting Density Control 45116.4.2 Conformation and Orientation of Recognition Units 45316.5 Transduction Schemes Based upon Grafted Biomolecules 46216.5.1 Electrochemical-Based Sensors 46216.5.2 Field Effect Transistor Based Sensors 46316.5.3 SPR-Based Sensors 46516.5.4 Photoluminescence-Based Sensors 46616.5.5 SERS Sensors 46816.5.6 Microcantilever Sensors 46916.6 Conclusions 471Acknowledgments 472References 47217 Phenylboronic Acid and Polymer Brushes: An Attractive Combination with Many Possibilities 479Solmaz Hajizadeh and Bo Mattiasson17.1 Introduction: Polymer Brushes and Synthesis 47917.2 Boronic Acid Brushes 48117.3 Affinity Separation 48317.4 Sensors 48717.5 Biomedical Applications 49217.6 Conclusions 494References 49418 Smart Surfaces Modified with Phenylboronic Acid Containing Polymer Brushes 497Hongliang Liu, ShutaoWang, and Lei Jiang18.1 Introduction 49718.2 Molecular Mechanism of PBA-Based Smart Surfaces 49818.3 pH-Responsive Surfaces Modified with PBA Polymer Brush and Their Applications 50118.4 Sugar-Responsive SurfacesModified with PBA Polymer Brush and Their Applications 50318.5 PBA Polymer Brush–Based pH/Sugar Dual-Responsive OR Logic Gates and Their Applications 50418.6 PBA Polymer Brush-Based pH/Sugar Dual-Responsive AND Logic Gates and Their Applications 50618.7 PBA-Based Smart Systems beyond Polymer Brush and Their Applications 50918.8 Conclusion and Perspective 511References 51219 Polymer Brushes andMicroorganisms 515Madeleine Ramstedt19.1 Introduction 51519.1.1 Societal Relevance for Surfaces Interacting with Microbes 51519.1.2 Microorganisms 51619.2 Brushes and Microbes 51919.2.1 Adhesive Surfaces 52919.2.2 Antifouling Surfaces 53019.2.2.1 PEG-Based Brushes 53119.2.2.2 Zwitterionic Brushes 53319.2.2.3 Brush Density 53319.2.2.4 Interactive Forces 53519.2.2.5 Mechanical Interactions 53719.2.3 Killing Surfaces 53719.2.3.1 Antimicrobial Peptides 54019.2.4 Brushes and Fungi 54319.2.5 Brushes and Algae 54619.3 Conclusions and Future Perspectives 549Acknowledgments 551References 55220 Design of Polymer Brushes for Cell Culture and Cellular Delivery 557Danyang Li and Julien E. GautrotAbbreviations 55720.1 Introduction 55920.2 Protein-Resistant Polymer Brushes for Tissue Engineering and In Vitro Assays 56120.2.1 Design of Protein-Resistant Polymer Brushes 56120.2.2 Cell-Resistant Polymer Brushes 56520.2.3 Patterned Antifouling Brushes for the Development of Cell-Based Assays 56720.3 Designing Brush Chemistry to Control Cell Adhesion and Proliferation 57020.3.1 Polyelectrolyte Brushes for Cell Adhesion and Culture 57020.3.2 Control of Surface Hydrophilicity 57320.3.3 Surfaces with Controlled Stereochemistry 57420.3.4 Switchable Brushes Displaying Responsive Behavior for Cell Harvesting and Detachment 57620.4 Biofunctionalized Polymer Brushes to Regulate Cell Phenotype 58120.4.1 Protein Coupling to Polymer Brushes to Control Cell Adhesion 58120.4.2 Peptide-Functionalized Polymer Brushes to Regulate Cell Adhesion, Proliferation, Differentiation, and Migration 58320.5 Polymer Brushes for Drug and Gene Delivery Applications 58620.5.1 Polymer Brushes in Drug Delivery 58620.5.2 Polymer Brushes in Gene Delivery 59020.6 Summary 593Acknowledgments 593References 59321 DNA Brushes: Self-Assembly, Physicochemical Properties, and Applications 605Ursula Koniges, Sade Ruffin, and Rastislav Levicky21.1 Introduction 60521.2 Applications 60521.3 Preparation 60721.4 Physicochemical Properties of DNA Brushes 61021.5 Hybridization in DNA Brushes 61321.6 Other Bioprocesses in DNA Brushes 61821.7 Perspective 619Acknowledgments 620References 62122 DNA Brushes: Advances in Synthesis and Applications 627Renpeng Gu, Lei Tang, Isao Aritome, and Stefan Zauscher22.1 Introduction 62722.2 Synthesis of DNA Brushes 62822.2.1 Grafting-to Approaches 62822.2.1.1 Immobilization on Gold Thin Films 62822.2.1.2 Immobilization on Silicon-Based Substrates 63222.2.2 Grafting-from Approaches 63422.2.2.1 Surface-Initiated Enzymatic Polymerization 63422.2.2.2 Surface-Initiated Rolling Circle Amplification 63422.2.2.3 Surface-Initiated Hybridization Chain Reaction 63422.2.3 Synthesis of DNA Brushes on Curved Surfaces 63722.3 Properties and Applications of DNA Brushes 63722.3.1 The Effect of DNA-Modifying Enzymes on the DNA Brush Structure 63722.3.2 Stimulus-Responsive Conformational Changes of DNA Brushes 63922.3.3 DNA Brush for Cell-Free Surface Protein Expression 64322.3.4 DNA Brush-Modified Nanoparticles for Biomedical Applications 64522.4 Conclusion and Outlook 649References 64923 Membrane Materials Form Polymer Brush Nanoparticles 655Erica Green, Emily Fullwood, Julieann Selden, and Ilya Zharov23.1 Introduction 65523.2 Colloidal Membranes Pore-Filled with Polymer Brushes 65723.2.1 Preparation of Silica Colloidal Membranes 65723.2.2 PAAM Brush-Filled Silica Colloidal Membranes 65823.2.3 PDMAEMA Brush-Filled Silica Colloidal Membranes 65923.2.4 PNIPAAM brush-filled silica colloidal membranes 66423.2.5 Polyalanine Brush-Filled Silica Colloidal Membranes 66623.2.6 PMMA Brush-Filled SiO2@Au Colloidal Membranes 67023.2.7 Colloidal Membranes Filled with Polymers Brushes Carrying Chiral Groups 67223.2.8 pSPM and pSSA Brush-Filled Colloidal Nanopores 67323.3 Self-Assembled PBNPs Membranes 67623.3.1 PDMAEMA/PSPM Membranes 67623.3.2 PHEMA Membranes 67823.3.3 pSPM and pSSA Membranes 68023.4 Summary 683References 68324 Responsive Polymer Networks and Brushes for Active Plasmonics 687Nestor Gisbert Quilis, Nityanand Sharma, Stefan Fossati,Wolfgang Knoll, and Jakub Dostalek24.1 Introduction 68724.2 Tuning Spectrum of Surface Plasmon Modes 68824.3 Polymers Used for Actuating of Plasmonic Structures 69224.3.1 Temperature-Responsive Polymers 69224.3.2 Optical Stimulus 69424.3.3 Electrochemical Stimulus 69524.3.4 Chemical Stimulus 69624.4 Imprinted Thermoresponsive Hydrogel Nanopillars 69724.5 Thermoresponsive Hydrogel Nanogratings Fabricated by UV Laser Interference Lithography 69924.6 Electrochemically Responsive Hydrogel Microgratings Prepared by UV Photolithography 70224.7 Conclusions 705Acknowledgments 706References 70625 Polymer Brushes as Interfacial Materials for Soft Metal Conductors and Electronics 709Casey Yan and Zijian Zheng25.1 Introduction 70925.2 Mechanisms of Polymer-Assisted Metal Deposition 71225.3 Role of Polymer Brushes 71625.4 Selection Criterion of Polymer Brushes Enabling PAMD 71625.5 Strategies to Fabricate Patterned Metal Conductors 71725.6 PAMD on Different Substrates and Their Applications in Soft Electronics 72025.6.1 On Textiles 72025.6.2 On Plastic Thin films 72125.6.3 On Elastomers 72425.6.4 On Sponges 72825.7 Conclusion, Prospects, and Challenges 731References 73226 Nanoarchitectonic Design of Complex Materials Using Polymer Brushes as Structural and Functional Units 735M. Lorena Cortez, Gisela D´ýaz,Waldemar A. Marmisoll´e, Juan M. Giussi, and Omar Azzaroni26.1 Introduction 73526.2 Nanoparticles at Spherical Polymer Brushes: Hierarchical Nanoarchitectonic Construction of Complex Functional Materials 73626.3 Nanotube and Nanowire Forests Bearing Polymer Brushes 73726.3.1 Polymer Brushes on Surfaces DisplayingMicrotopographical Hierarchical Arrays 73826.3.2 Environmentally Responsive Electrospun Nanofibers 74026.4 Fabrication of Free-Standing “Soft” Micro- and Nanoobjects Using Polymer Brushes 74126.5 Solid-State Polymer Electrolytes Based on Polymer Brush–Modified Colloidal Crystals 74326.6 Proton-Conducting Membranes with Enhanced Properties Using Polymer Brushes 74526.7 Hybrid Architectures Combining Mesoporous Materials and Responsive Polymer Brushes: Gated Molecular Transport Systems and Controlled Delivery Vehicles 74726.8 Ensembles of Metal NanoparticlesModified with Polymer Brushes 75026.9 Conclusions 754Acknowledgments 755References 755Index 759