<p>Volume 1</p> <p>Preface xxi</p> <p>List of Contributors xxiii</p> <p><b>1 Functionalization of Surfaces Using Polymer Brushes: An Overview of Techniques, Strategies, and</b> <b>Approaches 1<br /></b><i>Juan M. Giussi,M. Lorena Cortez,Waldemar A. Marmisoll´e, and Omar Azzaroni</i></p> <p>1.1 Introduction: Fundamental Notions and Concepts 1</p> <p>1.2 Preparation of Polymer Brushes on Solid Substrates 4</p> <p>1.3 Preparation of Polymer Brushes by the “Grafting-To” Method 5</p> <p>1.4 Polymer Brushes by the “Grafting-From” Method 9</p> <p>1.4.1 Surface-Initiated Atom Transfer Radical Polymerization 9</p> <p>1.4.2 Surface-Initiated Reversible-Addition Fragmentation Chain Transfer Polymerization 10</p> <p>1.4.3 Surface-Initiated Nitroxide-Mediated Polymerization 13</p> <p>1.4.4 Surface-Initiated Photoiniferter-Mediated Polymerization 13</p> <p>1.4.5 Surface-Initiated Living Ring-Opening Polymerization 15</p> <p>1.4.6 Surface-Initiated Ring-Opening Metathesis Polymerization 17</p> <p>1.4.7 Surface-Initiated Anionic Polymerization 18</p> <p>1.5 Conclusions 20</p> <p>Acknowledgments 21</p> <p>References 21</p> <p><b>2 Polymer Brushes by AtomTransfer Radical Polymerization 29<br /></b><i>Guojun Xie, Amir Khabibullin, Joanna Pietrasik, Jiajun Yan, and KrzysztofMatyjaszewski</i></p> <p>2.1 Structure of Brushes 29</p> <p>2.2 Synthesis of Polymer Brushes 31</p> <p>2.2.1 Grafting through 31</p> <p>2.2.2 Grafting to 32</p> <p>2.2.3 Grafting from 32</p> <p>2.3 ATRP Fundamentals 33</p> <p>2.4 Molecular Bottlebrushes by ATRP 38</p> <p>2.4.1 Introduction 38</p> <p>2.4.2 Star-Like Brushes 40</p> <p>2.4.3 Blockwise Brushes 42</p> <p>2.4.4 Brushes with Tunable Grafting Density 45</p> <p>2.4.5 Brushes with Block Copolymer Side Chains 46</p> <p>2.4.6 Functionalities and Properties of Brushes 50</p> <p>2.5 ATRP and Flat Surfaces 55</p> <p>2.5.1 Chemistry at Surface 55</p> <p>2.5.2 Grafting Density 55</p> <p>2.5.3 Architecture 56</p> <p>2.5.4 Applications 57</p> <p>2.6 ATRP and Nanoparticles 58</p> <p>2.6.1 Chemistry 58</p> <p>2.6.2 Architecture 59</p> <p>2.6.3 Applications 61</p> <p>2.7 ATRP and Concave Surfaces 63</p> <p>2.8 ATRP and Templates 63</p> <p>2.8.1 Templates from Networks 63</p> <p>2.8.2 Templates from Brushes 64</p> <p>2.9 Templates from Stars 65</p> <p>2.10 Bio-Related Polymer Brushes 66</p> <p>2.11 Stimuli-Responsive Polymer Brushes 74</p> <p>2.11.1 Stimuli-Responsive Solutions 76</p> <p>2.11.2 Stimuli-Responsive Surfaces 78</p> <p>2.12 Conclusion 79</p> <p>Acknowledgments 80</p> <p>References 80</p> <p><b>3 Polymer Brushes by Surface-Mediated RAFT Polymerization for Biological Functions 97<br /></b><i>Tuncer Caykara</i></p> <p>3.1 Introduction 97</p> <p>3.2 Polymer Brushes via the Surface-Initiated RAFT Polymerization Process 99</p> <p>3.3 Polymer Brushes via the Interface-Mediated RAFT Polymerization Process 101</p> <p>3.3.1 pH-Responsive Brushes 102</p> <p>3.3.2 Temperature-Responsive Brushes 106</p> <p>3.3.3 Polymer Brushes on Gold Surface 110</p> <p>3.3.4 Polymer Brushes on Nanoparticles 114</p> <p>3.3.5 Micropatterned Polymer Brushes 115</p> <p>3.4 Summary 117</p> <p>References 119</p> <p><b>4 Electro-Induced Copper-Catalyzed Surface Modification with Monolayer and Polymer Brush 123<br /></b><i>Bin Li and Feng Zhou</i></p> <p>4.1 Introduction 123</p> <p>4.2 “Electro-Click” Chemistry 124</p> <p>4.3 Electrochemically Induced Surface-Initiated Atom Transfer Radical Polymerization 129</p> <p>4.4 Possible Combination of eATRP and “e-Click” Chemistry on Surface 136</p> <p>4.5 Surface Functionality 136</p> <p>4.6 Summary 137</p> <p>Acknowledgments 138</p> <p>References 138</p> <p><b>5 Polymer Brushes on Flat and Curved Substrates:What Can be Learned fromMolecular Dynamics</b> <b>Simulations 141<br /></b><i>K. Binder, S.A. Egorov, and A.Milchev</i></p> <p>5.1 Introduction 141</p> <p>5.2 Molecular Dynamics Methods: A Short “Primer” 144</p> <p>5.3 The Standard Bead Spring Model for Polymer Chains 148</p> <p>5.4 Cylindrical and Spherical Polymer Brushes 150</p> <p>5.5 Interaction of Brushes with Free Chains 152</p> <p>5.6 Summary 153</p> <p>Acknowledgments 156</p> <p>References 157</p> <p><b>6 Modeling of Chemical Equilibria in Polymer and Polyelectrolyte Brushes 161<br /></b><i>Rikkert J. Nap,Mario Tagliazucchi, Estefania Gonzalez Solveyra, Chun-lai Ren, Mark J. Uline, and Igal</i> <i>Szleifer</i></p> <p>6.1 Introduction 161</p> <p>6.2 Theoretical Approach 163</p> <p>6.3 Applications of the Molecular Theory 177</p> <p>6.3.1 Acid–Base Equilibrium in Polyelectrolyte Brushes 178</p> <p>6.3.1.1 Effect of Salt Concentration and pH 178</p> <p>6.3.1.2 Effect of Polymer Density and Geometry 184</p> <p>6.3.2 Competition between Chemical Equilibria and Physical Interactions 186</p> <p>6.3.2.1 Brushes of Strong Polyelectrolytes 186</p> <p>6.3.2.2 Brushes ofWeak Polyelectrolytes: Self-Assembly in Charge-Regulating Systems 189</p> <p>6.3.2.3 Redox-Active Polyelectrolyte Brushes 193</p> <p>6.3.3 End-Tethered Single Stranded DNA in Aqueous Solutions 195</p> <p>6.3.4 Ligand–Receptor Binding and Protein Adsorption to Polymer Brushes 201</p> <p>6.3.5 Adsorption Equilibrium of Polymer Chains through Terminal Segments: Grafting-to Formation of Polymer Brushes 207</p> <p>6.4 Summary and Conclusion 212</p> <p>Acknowledgments 216</p> <p>References 216</p> <p><b>7 Brushes of Linear and Dendritically Branched Polyelectrolytes 223<br /></b><i>E. B. Zhulina, F. A. M. Leermakers, and O. V. Borisov</i></p> <p>7.1 Introduction 223</p> <p>7.2 Analytical SCF Theory of Brushes Formed by Linear and Branched Polyions 224</p> <p>7.2.1 Dendron Architecture and System Parameters 225</p> <p>7.2.2 Analytical SCF Formalism 226</p> <p>7.3 Planar Brush of PE Dendrons with an Arbitrary Architecture 229</p> <p>7.3.1 Asymptotic Dependences for Brush Thickness H 231</p> <p>7.4 Planar Brush of Star-Like Polyelectrolytes 232</p> <p>7.5 Threshold of Dendron Gaussian Elasticity 234</p> <p>7.6 Scaling-Type Diagrams of States for Brushes of Linear and Branched Polyions 235</p> <p>7.7 Numerical SF-SCF Model of Dendron Brush 236</p> <p>7.8 Conclusions 238</p> <p>References 239</p> <p><b>8 Vapor Swelling of Hydrophilic Polymer Brushes 243<br /></b><i>Casey J. Galvin and Jan Genzer</i></p> <p>8.1 Introduction 243</p> <p>8.2 Experimental 245</p> <p>8.2.1 General Methods 245</p> <p>8.2.2 Synthesis of Poly((2-dimethylamino)ethyl methacrylate) Brushes with a Gradient in Grafting Density 245</p> <p>8.2.3 Synthesis of Poly(2-(diethylamino)ethyl methacrylate) Brushes 245</p> <p>8.2.4 Chemical Modification of Poly((2-dimethylamino)ethyl methacrylate) Brushes 246</p> <p>8.2.5 Bulk Synthesis of PDMAEMA 246</p> <p>8.2.6 Preparation of Spuncast PDMAEMA Films 246</p> <p>8.2.7 Chemical Modification of Spuncast PDMAEMA Film 247</p> <p>8.2.8 Spectroscopic EllipsometryMeasurements under Controlled Humidity Conditions 247</p> <p>8.2.9 Spectroscopic EllipsometryMeasurements of Alcohol Exposure 247</p> <p>8.2.10 Fitting Spectroscopic Ellipsometry Data 248</p> <p>8.2.11 Infrared Variable Angle Spectroscopic Ellipsometry 248</p> <p>8.3 Results and Discussion 248</p> <p>8.3.1 Comparing Polymer Brush and Spuncast Polymer Film Swelling 250</p> <p>8.3.2 Influence of Side Chain Chemistry on Polymer Brush Vapor Swelling 252</p> <p>8.3.3 Influence of Solvent Vapor Chemistry on Polymer Brush Vapor Swelling 256</p> <p>8.3.4 Influence of Grafting Density on Polymer Brush Vapor Swelling 259</p> <p>8.4 Conclusion 262</p> <p>8.A.1 Appendix 263</p> <p>8.A.1.1 Mole Fraction Calculation 263</p> <p>8.A.1.2 Water Cluster Number Calculation 264</p> <p>Acknowledgments 265</p> <p>References 265</p> <p><b>9 Temperature Dependence of the Swelling and Surface Wettability of Dense Polymer Brushes 267<br /></b><i>Pengyu Zhuang, Ali Dirani, Karine Glinel, and AlainM. Jonas</i></p> <p>9.1 Introduction 267</p> <p>9.2 The Swelling Coefficient of a Polymer Brush Mirrors Its Volume Hydrophilicity 269</p> <p>9.3 The Cosine of the Contact Angle ofWater on aWater-Equilibrated Polymer Brush Defines Its Surface Hydrophilicity 270</p> <p>9.4 Case Study: Temperature-Dependent Surface hydrophilicity of Dense PNIPAM Brushes 272</p> <p>9.5 Case Study: Temperature-Dependent Swelling and Volume Hydrophilicity of Dense PNIPAMBrushes 274</p> <p>9.6 Thermoresponsive Poly(oligo(ethylene oxide)methacrylate) Copolymer Brushes: Versatile Functional Alternatives to PNIPAM 277</p> <p>9.7 Surface and Volume Hydrophilicity of Nonthermoresponsive Poly(oligo(ethylene oxide)methacrylate) Copolymer Brushes 279</p> <p>9.8 Conclusions 282</p> <p>Acknowledgments 283</p> <p>References 283</p> <p><b>10 Functional Biointerfaces Tailored by “Grafting-To”Brushes 287<br /></b><i>Eva Bittrich, Manfred Stamm, and Petra Uhlmann</i></p> <p>10.1 Introduction 287</p> <p>10.2 Part I: Polymer Brush Architectures 288</p> <p>10.2.1 Design of Physicochemical Interfaces by Polymer Brushes 288</p> <p>10.2.1.1 Stimuli-Responsive Homopolymer Brushes 288</p> <p>10.2.1.2 Combination of Responses Using Mixed Polymer Brushes 290</p> <p>10.2.1.3 Stimuli-Responsive Gradient Brushes 293</p> <p>10.2.2 Modification of Polymer Brushes by Click Chemistry 293</p> <p>10.2.2.1 Definition of Click Chemistry 293</p> <p>10.2.2.2 Modification of End Groups of Grafted PNIPAAm Chains 295</p> <p>10.2.3 Hybrid Brush Nanostructures 297</p> <p>10.2.3.1 Nanoparticles Immobilized at Polymer Brushes 298</p> <p>10.2.3.2 Sculptured Thin Films Grafted with Polymer Brushes 300</p> <p>10.3 Part II: Actuating Biomolecule Interactions with Surfaces 303</p> <p>10.3.1 Adsorption of Proteins to Polymer Brush Surfaces 303</p> <p>10.3.1.1 Calculation of the Adsorbed Amount of Protein from Ellipsometric Experiments 305</p> <p>10.3.1.2 Preventing Protein Adsorption 306</p> <p>10.3.1.3 Adsorption at Polyelectrolyte Brushes 310</p> <p>10.3.2 Polymer Brushes as Interfaces for Cell Adhesion and Interaction 313</p> <p>10.3.2.1 Cell Adhesion on Stimuli-Responsive Polymer Surfaces Based on PNIPAAm Brushes 315</p> <p>10.3.2.2 Growth Factors on Polymer Brushes 318</p> <p>10.4 Conclusion and Outlook 320</p> <p>Acknowledgments 321</p> <p>References 321</p> <p><b>11 Glycopolymer Brushes Presenting Sugars in Their Natural Form: Synthesis and Applications 333<br /></b><i>Kai Yu and Jayachandran N. Kizhakkedathu</i></p> <p>11.1 Introduction and Background 333</p> <p>11.2 Results and Discussion 334</p> <p>11.2.1 Synthesis of Glycopolymer Brushes 334</p> <p>11.2.1.1 Synthesis of N-Substituted Acrylamide Derivatives of Glycomonomers 334</p> <p>11.2.1.2 Synthesis and Characterization of Glycopolymer Brushes on Gold Chip and SiliconWafer 334</p> <p>11.2.1.3 Synthesis and Characterization of Glycopolymer Brushes on Polystyrene Particles 335</p> <p>11.2.1.4 Synthesis and Characterization of Glycopolymer Brushes with Variation in the Composition of Carbohydrate Residues on SPR Chip 338</p> <p>11.2.1.5 Preparation of Glycopolymer Brushes-Modified Particles with Different Grafting Density (Conformation) 338</p> <p>11.2.2 Applications of Glycopolymer Brushes 341</p> <p>11.2.2.1 Antithrombotic Surfaces Based on Glycopolymer Brushes 341</p> <p>11.2.2.2 Glycopolymer Brushes Based Carbohydrate Arrays to Modulate Multivalent Protein Binding on Surfaces 345</p> <p>11.2.2.3 Modulation of Innate Immune Response by the Conformation and Chemistry of Glycopolymer Brushes 351</p> <p>11.3 Conclusions 356</p> <p>Acknowledgments 357</p> <p>References 357</p> <p><b>12 Thermoresponsive Polymer Brushes for Thermally Modulated Cell Adhesion and Detachment 361<br /></b><i>Kenichi Nagase and Teruo Okano</i></p> <p>12.1 Introduction 361</p> <p>12.2 Thermoresponsive Polymer Hydrogel-Modified Surfaces for Cell Adhesion and Detachment 362</p> <p>12.3 Thermoresponsive Polymer Brushes Prepared Using ATRP 363</p> <p>12.4 Thermoresponsive Polymer Brushes Prepared by RAFT Polymerization 368</p> <p>12.5 Conclusions 372</p> <p>Acknowledgments 372</p> <p>References 372</p> <p>Volume 2</p> <p>Preface xxi</p> <p>List of Contributors xxiii</p> <p><b>13 Biomimetic Anchors for Antifouling Polymer Brush Coatings 377<br /></b><i>Dicky Pranantyo, Li Qun Xu, En-Tang Kang, Koon-Gee Neoh, and Serena Lay-Ming Teo</i></p> <p>13.1 Introduction to Biofouling Management 377</p> <p>13.2 Polymer Brushes for Surface Functionalization 378</p> <p>13.3 Biomimetic Anchors for Antifouling Polymer Brushes 379</p> <p>13.3.1 Mussel Adhesive-Inspired Dopamine Anchors 379</p> <p>13.3.1.1 Antifouling Polymer Brushes Prepared via the “Grafting-To” Approach on (poly)Dopamine Anchor 383</p> <p>13.3.1.2 Antifouling Polymer Brushes Prepared via the “Grafting-From” Approach on (poly)Dopamine Anchor 386</p> <p>13.3.1.3 Direct Grafting of Antifouling Polymer Brushes Containing Anchorable Dopamine-Derived Functionalities 389</p> <p>13.3.2 (Poly)phenolic Anchors for Antifouling Polymer Brushes 391</p> <p>13.3.3 Biomolecular Anchors for Antifouling Polymer Brushes 393</p> <p>13.4 Barnacle Cement as Anchor for Antifouling Polymer Brushes 397</p> <p>13.5 Conclusion and Outlooks 399</p> <p>References 400</p> <p><b>14 Protein Adsorption Process Based on Molecular Interactions at Well-Defined Polymer Brush Surfaces 405<br /></b><i>Sho Sakata, Yuuki Inoue, and Kazuhiko Ishihara</i></p> <p>14.1 Introduction 405</p> <p>14.2 Utility of Polymer Brush Layers as Highly Controllable Polymer Surfaces 406</p> <p>14.3 Performance of Polymer Brush Surfaces as Antifouling Biointerfaces 408</p> <p>14.4 Elucidation of Protein Adsorption Based on Molecular Interaction Forces 412</p> <p>14.5 Concluding Remarks 416</p> <p>References 417</p> <p><b>15 Are Lubricious Polymer Brushes Antifouling? Are Antifouling Polymer Brushes Lubricious? 421<br /></b><i>Edmondo M. Benetti and Nicholas D. Spencer</i></p> <p>15.1 Introduction 421</p> <p>15.2 Poly(ethylene glycol) Brushes 422</p> <p>15.3 Beyond Simple PEG Brushes 424</p> <p>15.4 Conclusion 429</p> <p>References 429</p> <p><b>16 Biofunctionalized Brush Surfaces for Biomolecular Sensing 433<br /></b><i>Shuaidi Zhang and Vladimir V. Tsukruk</i></p> <p>16.1 Introduction 433</p> <p>16.2 Biorecognition Units 435</p> <p>16.2.1 Antibodies 435</p> <p>16.2.2 Antibody Fragments 435</p> <p>16.2.3 Aptamers 437</p> <p>16.2.4 Peptide Aptamers 438</p> <p>16.2.5 Enzymes 438</p> <p>16.2.6 Peptide Nucleic Acid, Lectin, and Molecular Imprinted Polymers 439</p> <p>16.3 Immobilization Strategy 439</p> <p>16.3.1 Through Direct Covalent Linkage 440</p> <p>16.3.1.1 Thiolated Aptamers on Noble Metal 440</p> <p>16.3.1.2 General Activated Surface Chemistry 442</p> <p>16.3.1.3 Diels–Alder Cycloaddition 444</p> <p>16.3.1.4 Staudinger Ligation 444</p> <p>16.3.1.5 1,3-Dipolar Cycloaddition 446</p> <p>16.3.2 Through Affinity Tags 447</p> <p>16.3.2.1 Biotin–Avidin/Streptavidin Pairing 447</p> <p>16.3.2.2 NTA–Ni2+–Histidine Pairing 448</p> <p>16.3.2.3 Protein A/Protein G – Fc Pairing 449</p> <p>16.3.2.4 Oligonucleotide Hybridization 450</p> <p>16.4 Microstructure and Morphology of Biobrush Layers 451</p> <p>16.4.1 Grafting Density Control 451</p> <p>16.4.2 Conformation and Orientation of Recognition Units 453</p> <p>16.5 Transduction Schemes Based upon Grafted Biomolecules 462</p> <p>16.5.1 Electrochemical-Based Sensors 462</p> <p>16.5.2 Field Effect Transistor Based Sensors 463</p> <p>16.5.3 SPR-Based Sensors 465</p> <p>16.5.4 Photoluminescence-Based Sensors 466</p> <p>16.5.5 SERS Sensors 468</p> <p>16.5.6 Microcantilever Sensors 469</p> <p>16.6 Conclusions 471</p> <p>Acknowledgments 472</p> <p>References 472</p> <p><b>17 Phenylboronic Acid and Polymer Brushes: An Attractive Combination with Many Possibilities 479<br /></b><i>Solmaz Hajizadeh and Bo Mattiasson</i></p> <p>17.1 Introduction: Polymer Brushes and Synthesis 479</p> <p>17.2 Boronic Acid Brushes 481</p> <p>17.3 Affinity Separation 483</p> <p>17.4 Sensors 487</p> <p>17.5 Biomedical Applications 492</p> <p>17.6 Conclusions 494</p> <p>References 494</p> <p><b>18 Smart Surfaces Modified with Phenylboronic Acid Containing Polymer Brushes 497<br /></b><i>Hongliang Liu, ShutaoWang, and Lei Jiang</i></p> <p>18.1 Introduction 497</p> <p>18.2 Molecular Mechanism of PBA-Based Smart Surfaces 498</p> <p>18.3 pH-Responsive Surfaces Modified with PBA Polymer Brush and Their Applications 501</p> <p>18.4 Sugar-Responsive SurfacesModified with PBA Polymer Brush and Their Applications 503</p> <p>18.5 PBA Polymer Brush–Based pH/Sugar Dual-Responsive OR Logic Gates and Their Applications 504</p> <p>18.6 PBA Polymer Brush-Based pH/Sugar Dual-Responsive AND Logic Gates and Their Applications 506</p> <p>18.7 PBA-Based Smart Systems beyond Polymer Brush and Their Applications 509</p> <p>18.8 Conclusion and Perspective 511</p> <p>References 512</p> <p><b>19 Polymer Brushes andMicroorganisms 515<br /></b><i>Madeleine Ramstedt</i></p> <p>19.1 Introduction 515</p> <p>19.1.1 Societal Relevance for Surfaces Interacting with Microbes 515</p> <p>19.1.2 Microorganisms 516</p> <p>19.2 Brushes and Microbes 519</p> <p>19.2.1 Adhesive Surfaces 529</p> <p>19.2.2 Antifouling Surfaces 530</p> <p>19.2.2.1 PEG-Based Brushes 531</p> <p>19.2.2.2 Zwitterionic Brushes 533</p> <p>19.2.2.3 Brush Density 533</p> <p>19.2.2.4 Interactive Forces 535</p> <p>19.2.2.5 Mechanical Interactions 537</p> <p>19.2.3 Killing Surfaces 537</p> <p>19.2.3.1 Antimicrobial Peptides 540</p> <p>19.2.4 Brushes and Fungi 543</p> <p>19.2.5 Brushes and Algae 546</p> <p>19.3 Conclusions and Future Perspectives 549</p> <p>Acknowledgments 551</p> <p>References 552</p> <p><b>20 Design of Polymer Brushes for Cell Culture and Cellular Delivery 557<br /></b><i>Danyang Li and Julien E. Gautrot</i></p> <p>Abbreviations 557</p> <p>20.1 Introduction 559</p> <p>20.2 Protein-Resistant Polymer Brushes for Tissue Engineering and In Vitro Assays 561</p> <p>20.2.1 Design of Protein-Resistant Polymer Brushes 561</p> <p>20.2.2 Cell-Resistant Polymer Brushes 565</p> <p>20.2.3 Patterned Antifouling Brushes for the Development of Cell-Based Assays 567</p> <p>20.3 Designing Brush Chemistry to Control Cell Adhesion and Proliferation 570</p> <p>20.3.1 Polyelectrolyte Brushes for Cell Adhesion and Culture 570</p> <p>20.3.2 Control of Surface Hydrophilicity 573</p> <p>20.3.3 Surfaces with Controlled Stereochemistry 574</p> <p>20.3.4 Switchable Brushes Displaying Responsive Behavior for Cell Harvesting and Detachment 576</p> <p>20.4 Biofunctionalized Polymer Brushes to Regulate Cell Phenotype 581</p> <p>20.4.1 Protein Coupling to Polymer Brushes to Control Cell Adhesion 581</p> <p>20.4.2 Peptide-Functionalized Polymer Brushes to Regulate Cell Adhesion, Proliferation, Differentiation, and Migration 583</p> <p>20.5 Polymer Brushes for Drug and Gene Delivery Applications 586</p> <p>20.5.1 Polymer Brushes in Drug Delivery 586</p> <p>20.5.2 Polymer Brushes in Gene Delivery 590</p> <p>20.6 Summary 593</p> <p>Acknowledgments 593</p> <p>References 593</p> <p><b>21 DNA Brushes: Self-Assembly, Physicochemical Properties, and Applications 605<br /></b><i>Ursula Koniges, Sade Ruffin, and Rastislav Levicky</i></p> <p>21.1 Introduction 605</p> <p>21.2 Applications 605</p> <p>21.3 Preparation 607</p> <p>21.4 Physicochemical Properties of DNA Brushes 610</p> <p>21.5 Hybridization in DNA Brushes 613</p> <p>21.6 Other Bioprocesses in DNA Brushes 618</p> <p>21.7 Perspective 619</p> <p>Acknowledgments 620</p> <p>References 621</p> <p><b>22 DNA Brushes: Advances in Synthesis and Applications 627<br /></b><i>Renpeng Gu, Lei Tang, Isao Aritome, and Stefan Zauscher</i></p> <p>22.1 Introduction 627</p> <p>22.2 Synthesis of DNA Brushes 628</p> <p>22.2.1 Grafting-to Approaches 628</p> <p>22.2.1.1 Immobilization on Gold Thin Films 628</p> <p>22.2.1.2 Immobilization on Silicon-Based Substrates 632</p> <p>22.2.2 Grafting-from Approaches 634</p> <p>22.2.2.1 Surface-Initiated Enzymatic Polymerization 634</p> <p>22.2.2.2 Surface-Initiated Rolling Circle Amplification 634</p> <p>22.2.2.3 Surface-Initiated Hybridization Chain Reaction 634</p> <p>22.2.3 Synthesis of DNA Brushes on Curved Surfaces 637</p> <p>22.3 Properties and Applications of DNA Brushes 637</p> <p>22.3.1 The Effect of DNA-Modifying Enzymes on the DNA Brush Structure 637</p> <p>22.3.2 Stimulus-Responsive Conformational Changes of DNA Brushes 639</p> <p>22.3.3 DNA Brush for Cell-Free Surface Protein Expression 643</p> <p>22.3.4 DNA Brush-Modified Nanoparticles for Biomedical Applications 645</p> <p>22.4 Conclusion and Outlook 649</p> <p>References 649</p> <p><b>23 Membrane Materials Form Polymer Brush Nanoparticles 655<br /></b><i>Erica Green, Emily Fullwood, Julieann Selden, and Ilya Zharov</i></p> <p>23.1 Introduction 655</p> <p>23.2 Colloidal Membranes Pore-Filled with Polymer Brushes 657</p> <p>23.2.1 Preparation of Silica Colloidal Membranes 657</p> <p>23.2.2 PAAM Brush-Filled Silica Colloidal Membranes 658</p> <p>23.2.3 PDMAEMA Brush-Filled Silica Colloidal Membranes 659</p> <p>23.2.4 PNIPAAM brush-filled silica colloidal membranes 664</p> <p>23.2.5 Polyalanine Brush-Filled Silica Colloidal Membranes 666</p> <p>23.2.6 PMMA Brush-Filled SiO2@Au Colloidal Membranes 670</p> <p>23.2.7 Colloidal Membranes Filled with Polymers Brushes Carrying Chiral Groups 672</p> <p>23.2.8 pSPM and pSSA Brush-Filled Colloidal Nanopores 673</p> <p>23.3 Self-Assembled PBNPs Membranes 676</p> <p>23.3.1 PDMAEMA/PSPM Membranes 676</p> <p>23.3.2 PHEMA Membranes 678</p> <p>23.3.3 pSPM and pSSA Membranes 680</p> <p>23.4 Summary 683</p> <p>References 683</p> <p><b>24 Responsive Polymer Networks and Brushes for Active Plasmonics 687<br /></b><i>Nestor Gisbert Quilis, Nityanand Sharma, Stefan Fossati,Wolfgang Knoll, and Jakub Dostalek</i></p> <p>24.1 Introduction 687</p> <p>24.2 Tuning Spectrum of Surface Plasmon Modes 688</p> <p>24.3 Polymers Used for Actuating of Plasmonic Structures 692</p> <p>24.3.1 Temperature-Responsive Polymers 692</p> <p>24.3.2 Optical Stimulus 694</p> <p>24.3.3 Electrochemical Stimulus 695</p> <p>24.3.4 Chemical Stimulus 696</p> <p>24.4 Imprinted Thermoresponsive Hydrogel Nanopillars 697</p> <p>24.5 Thermoresponsive Hydrogel Nanogratings Fabricated by UV Laser Interference Lithography 699</p> <p>24.6 Electrochemically Responsive Hydrogel Microgratings Prepared by UV Photolithography 702</p> <p>24.7 Conclusions 705</p> <p>Acknowledgments 706</p> <p>References 706</p> <p><b>25 Polymer Brushes as Interfacial Materials for Soft Metal Conductors and Electronics 709<br /></b><i>Casey Yan and Zijian Zheng</i></p> <p>25.1 Introduction 709</p> <p>25.2 Mechanisms of Polymer-Assisted Metal Deposition 712</p> <p>25.3 Role of Polymer Brushes 716</p> <p>25.4 Selection Criterion of Polymer Brushes Enabling PAMD 716</p> <p>25.5 Strategies to Fabricate Patterned Metal Conductors 717</p> <p>25.6 PAMD on Different Substrates and Their Applications in Soft Electronics 720</p> <p>25.6.1 On Textiles 720</p> <p>25.6.2 On Plastic Thin films 721</p> <p>25.6.3 On Elastomers 724</p> <p>25.6.4 On Sponges 728</p> <p>25.7 Conclusion, Prospects, and Challenges 731</p> <p>References 732</p> <p><b>26 Nanoarchitectonic Design of Complex Materials Using Polymer Brushes as Structural and Functional Units 735<br /></b><i>M. Lorena Cortez, Gisela D´yaz,Waldemar A. Marmisoll´e, Juan M. Giussi, and Omar Azzaroni</i></p> <p>26.1 Introduction 735</p> <p>26.2 Nanoparticles at Spherical Polymer Brushes: Hierarchical Nanoarchitectonic Construction of Complex Functional Materials 736</p> <p>26.3 Nanotube and Nanowire Forests Bearing Polymer Brushes 737</p> <p>26.3.1 Polymer Brushes on Surfaces DisplayingMicrotopographical Hierarchical Arrays 738</p> <p>26.3.2 Environmentally Responsive Electrospun Nanofibers 740</p> <p>26.4 Fabrication of Free-Standing “Soft” Micro- and Nanoobjects Using Polymer Brushes 741</p> <p>26.5 Solid-State Polymer Electrolytes Based on Polymer Brush–Modified Colloidal Crystals 743</p> <p>26.6 Proton-Conducting Membranes with Enhanced Properties Using Polymer Brushes 745</p> <p>26.7 Hybrid Architectures Combining Mesoporous Materials and Responsive Polymer Brushes: Gated Molecular Transport Systems and Controlled Delivery Vehicles 747</p> <p>26.8 Ensembles of Metal NanoparticlesModified with Polymer Brushes 750</p> <p>26.9 Conclusions 754</p> <p>Acknowledgments 755</p> <p>References 755</p> <p>Index 759</p>