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 1

Preface xxi

List of Contributors xxiii

1 Functionalization of Surfaces Using Polymer Brushes: An Overview of Techniques, Strategies, and Approaches 1
Juan M. Giussi,M. Lorena Cortez,Waldemar A. Marmisoll´e, and Omar Azzaroni

1.1 Introduction: Fundamental Notions and Concepts 1

1.2 Preparation of Polymer Brushes on Solid Substrates 4

1.3 Preparation of Polymer Brushes by the “Grafting-To” Method 5

1.4 Polymer Brushes by the “Grafting-From” Method 9

1.4.1 Surface-Initiated Atom Transfer Radical Polymerization 9

1.4.2 Surface-Initiated Reversible-Addition Fragmentation Chain Transfer Polymerization 10

1.4.3 Surface-Initiated Nitroxide-Mediated Polymerization 13

1.4.4 Surface-Initiated Photoiniferter-Mediated Polymerization 13

1.4.5 Surface-Initiated Living Ring-Opening Polymerization 15

1.4.6 Surface-Initiated Ring-Opening Metathesis Polymerization 17

1.4.7 Surface-Initiated Anionic Polymerization 18

1.5 Conclusions 20

Acknowledgments 21

References 21

2 Polymer Brushes by AtomTransfer Radical Polymerization 29
Guojun Xie, Amir Khabibullin, Joanna Pietrasik, Jiajun Yan, and KrzysztofMatyjaszewski

2.1 Structure of Brushes 29

2.2 Synthesis of Polymer Brushes 31

2.2.1 Grafting through 31

2.2.2 Grafting to 32

2.2.3 Grafting from 32

2.3 ATRP Fundamentals 33

2.4 Molecular Bottlebrushes by ATRP 38

2.4.1 Introduction 38

2.4.2 Star-Like Brushes 40

2.4.3 Blockwise Brushes 42

2.4.4 Brushes with Tunable Grafting Density 45

2.4.5 Brushes with Block Copolymer Side Chains 46

2.4.6 Functionalities and Properties of Brushes 50

2.5 ATRP and Flat Surfaces 55

2.5.1 Chemistry at Surface 55

2.5.2 Grafting Density 55

2.5.3 Architecture 56

2.5.4 Applications 57

2.6 ATRP and Nanoparticles 58

2.6.1 Chemistry 58

2.6.2 Architecture 59

2.6.3 Applications 61

2.7 ATRP and Concave Surfaces 63

2.8 ATRP and Templates 63

2.8.1 Templates from Networks 63

2.8.2 Templates from Brushes 64

2.9 Templates from Stars 65

2.10 Bio-Related Polymer Brushes 66

2.11 Stimuli-Responsive Polymer Brushes 74

2.11.1 Stimuli-Responsive Solutions 76

2.11.2 Stimuli-Responsive Surfaces 78

2.12 Conclusion 79

Acknowledgments 80

References 80

3 Polymer Brushes by Surface-Mediated RAFT Polymerization for Biological Functions 97
Tuncer Caykara

3.1 Introduction 97

3.2 Polymer Brushes via the Surface-Initiated RAFT Polymerization Process 99

3.3 Polymer Brushes via the Interface-Mediated RAFT Polymerization Process 101

3.3.1 pH-Responsive Brushes 102

3.3.2 Temperature-Responsive Brushes 106

3.3.3 Polymer Brushes on Gold Surface 110

3.3.4 Polymer Brushes on Nanoparticles 114

3.3.5 Micropatterned Polymer Brushes 115

3.4 Summary 117

References 119

4 Electro-Induced Copper-Catalyzed Surface Modification with Monolayer and Polymer Brush 123
Bin Li and Feng Zhou

4.1 Introduction 123

4.2 “Electro-Click” Chemistry 124

4.3 Electrochemically Induced Surface-Initiated Atom Transfer Radical Polymerization 129

4.4 Possible Combination of eATRP and “e-Click” Chemistry on Surface 136

4.5 Surface Functionality 136

4.6 Summary 137

Acknowledgments 138

References 138

5 Polymer Brushes on Flat and Curved Substrates:What Can be Learned fromMolecular Dynamics Simulations 141
K. Binder, S.A. Egorov, and A.Milchev

5.1 Introduction 141

5.2 Molecular Dynamics Methods: A Short “Primer” 144

5.3 The Standard Bead Spring Model for Polymer Chains 148

5.4 Cylindrical and Spherical Polymer Brushes 150

5.5 Interaction of Brushes with Free Chains 152

5.6 Summary 153

Acknowledgments 156

References 157

6 Modeling of Chemical Equilibria in Polymer and Polyelectrolyte Brushes 161
Rikkert J. Nap,Mario Tagliazucchi, Estefania Gonzalez Solveyra, Chun-lai Ren, Mark J. Uline, and Igal Szleifer

6.1 Introduction 161

6.2 Theoretical Approach 163

6.3 Applications of the Molecular Theory 177

6.3.1 Acid–Base Equilibrium in Polyelectrolyte Brushes 178

6.3.1.1 Effect of Salt Concentration and pH 178

6.3.1.2 Effect of Polymer Density and Geometry 184

6.3.2 Competition between Chemical Equilibria and Physical Interactions 186

6.3.2.1 Brushes of Strong Polyelectrolytes 186

6.3.2.2 Brushes ofWeak Polyelectrolytes: Self-Assembly in Charge-Regulating Systems 189

6.3.2.3 Redox-Active Polyelectrolyte Brushes 193

6.3.3 End-Tethered Single Stranded DNA in Aqueous Solutions 195

6.3.4 Ligand–Receptor Binding and Protein Adsorption to Polymer Brushes 201

6.3.5 Adsorption Equilibrium of Polymer Chains through Terminal Segments: Grafting-to Formation of Polymer Brushes 207

6.4 Summary and Conclusion 212

Acknowledgments 216

References 216

7 Brushes of Linear and Dendritically Branched Polyelectrolytes 223
E. B. Zhulina, F. A. M. Leermakers, and O. V. Borisov

7.1 Introduction 223

7.2 Analytical SCF Theory of Brushes Formed by Linear and Branched Polyions 224

7.2.1 Dendron Architecture and System Parameters 225

7.2.2 Analytical SCF Formalism 226

7.3 Planar Brush of PE Dendrons with an Arbitrary Architecture 229

7.3.1 Asymptotic Dependences for Brush Thickness H 231

7.4 Planar Brush of Star-Like Polyelectrolytes 232

7.5 Threshold of Dendron Gaussian Elasticity 234

7.6 Scaling-Type Diagrams of States for Brushes of Linear and Branched Polyions 235

7.7 Numerical SF-SCF Model of Dendron Brush 236

7.8 Conclusions 238

References 239

8 Vapor Swelling of Hydrophilic Polymer Brushes 243
Casey J. Galvin and Jan Genzer

8.1 Introduction 243

8.2 Experimental 245

8.2.1 General Methods 245

8.2.2 Synthesis of Poly((2-dimethylamino)ethyl methacrylate) Brushes with a Gradient in Grafting Density 245

8.2.3 Synthesis of Poly(2-(diethylamino)ethyl methacrylate) Brushes 245

8.2.4 Chemical Modification of Poly((2-dimethylamino)ethyl methacrylate) Brushes 246

8.2.5 Bulk Synthesis of PDMAEMA 246

8.2.6 Preparation of Spuncast PDMAEMA Films 246

8.2.7 Chemical Modification of Spuncast PDMAEMA Film 247

8.2.8 Spectroscopic EllipsometryMeasurements under Controlled Humidity Conditions 247

8.2.9 Spectroscopic EllipsometryMeasurements of Alcohol Exposure 247

8.2.10 Fitting Spectroscopic Ellipsometry Data 248

8.2.11 Infrared Variable Angle Spectroscopic Ellipsometry 248

8.3 Results and Discussion 248

8.3.1 Comparing Polymer Brush and Spuncast Polymer Film Swelling 250

8.3.2 Influence of Side Chain Chemistry on Polymer Brush Vapor Swelling 252

8.3.3 Influence of Solvent Vapor Chemistry on Polymer Brush Vapor Swelling 256

8.3.4 Influence of Grafting Density on Polymer Brush Vapor Swelling 259

8.4 Conclusion 262

8.A.1 Appendix 263

8.A.1.1 Mole Fraction Calculation 263

8.A.1.2 Water Cluster Number Calculation 264

Acknowledgments 265

References 265

9 Temperature Dependence of the Swelling and Surface Wettability of Dense Polymer Brushes 267
Pengyu Zhuang, Ali Dirani, Karine Glinel, and AlainM. Jonas

9.1 Introduction 267

9.2 The Swelling Coefficient of a Polymer Brush Mirrors Its Volume Hydrophilicity 269

9.3 The Cosine of the Contact Angle ofWater on aWater-Equilibrated Polymer Brush Defines Its Surface Hydrophilicity 270

9.4 Case Study: Temperature-Dependent Surface hydrophilicity of Dense PNIPAM Brushes 272

9.5 Case Study: Temperature-Dependent Swelling and Volume Hydrophilicity of Dense PNIPAMBrushes 274

9.6 Thermoresponsive Poly(oligo(ethylene oxide)methacrylate) Copolymer Brushes: Versatile Functional Alternatives to PNIPAM 277

9.7 Surface and Volume Hydrophilicity of Nonthermoresponsive Poly(oligo(ethylene oxide)methacrylate) Copolymer Brushes 279

9.8 Conclusions 282

Acknowledgments 283

References 283

10 Functional Biointerfaces Tailored by “Grafting-To”Brushes 287
Eva Bittrich, Manfred Stamm, and Petra Uhlmann

10.1 Introduction 287

10.2 Part I: Polymer Brush Architectures 288

10.2.1 Design of Physicochemical Interfaces by Polymer Brushes 288

10.2.1.1 Stimuli-Responsive Homopolymer Brushes 288

10.2.1.2 Combination of Responses Using Mixed Polymer Brushes 290

10.2.1.3 Stimuli-Responsive Gradient Brushes 293

10.2.2 Modification of Polymer Brushes by Click Chemistry 293

10.2.2.1 Definition of Click Chemistry 293

10.2.2.2 Modification of End Groups of Grafted PNIPAAm Chains 295

10.2.3 Hybrid Brush Nanostructures 297

10.2.3.1 Nanoparticles Immobilized at Polymer Brushes 298

10.2.3.2 Sculptured Thin Films Grafted with Polymer Brushes 300

10.3 Part II: Actuating Biomolecule Interactions with Surfaces 303

10.3.1 Adsorption of Proteins to Polymer Brush Surfaces 303

10.3.1.1 Calculation of the Adsorbed Amount of Protein from Ellipsometric Experiments 305

10.3.1.2 Preventing Protein Adsorption 306

10.3.1.3 Adsorption at Polyelectrolyte Brushes 310

10.3.2 Polymer Brushes as Interfaces for Cell Adhesion and Interaction 313

10.3.2.1 Cell Adhesion on Stimuli-Responsive Polymer Surfaces Based on PNIPAAm Brushes 315

10.3.2.2 Growth Factors on Polymer Brushes 318

10.4 Conclusion and Outlook 320

Acknowledgments 321

References 321

11 Glycopolymer Brushes Presenting Sugars in Their Natural Form: Synthesis and Applications 333
Kai Yu and Jayachandran N. Kizhakkedathu

11.1 Introduction and Background 333

11.2 Results and Discussion 334

11.2.1 Synthesis of Glycopolymer Brushes 334

11.2.1.1 Synthesis of N-Substituted Acrylamide Derivatives of Glycomonomers 334

11.2.1.2 Synthesis and Characterization of Glycopolymer Brushes on Gold Chip and SiliconWafer 334

11.2.1.3 Synthesis and Characterization of Glycopolymer Brushes on Polystyrene Particles 335

11.2.1.4 Synthesis and Characterization of Glycopolymer Brushes with Variation in the Composition of Carbohydrate Residues on SPR Chip 338

11.2.1.5 Preparation of Glycopolymer Brushes-Modified Particles with Different Grafting Density (Conformation) 338

11.2.2 Applications of Glycopolymer Brushes 341

11.2.2.1 Antithrombotic Surfaces Based on Glycopolymer Brushes 341

11.2.2.2 Glycopolymer Brushes Based Carbohydrate Arrays to Modulate Multivalent Protein Binding on Surfaces 345

11.2.2.3 Modulation of Innate Immune Response by the Conformation and Chemistry of Glycopolymer Brushes 351

11.3 Conclusions 356

Acknowledgments 357

References 357

12 Thermoresponsive Polymer Brushes for Thermally Modulated Cell Adhesion and Detachment 361
Kenichi Nagase and Teruo Okano

12.1 Introduction 361

12.2 Thermoresponsive Polymer Hydrogel-Modified Surfaces for Cell Adhesion and Detachment 362

12.3 Thermoresponsive Polymer Brushes Prepared Using ATRP 363

12.4 Thermoresponsive Polymer Brushes Prepared by RAFT Polymerization 368

12.5 Conclusions 372

Acknowledgments 372

References 372

Volume 2

Preface xxi

List of Contributors xxiii

13 Biomimetic Anchors for Antifouling Polymer Brush Coatings 377
Dicky Pranantyo, Li Qun Xu, En-Tang Kang, Koon-Gee Neoh, and Serena Lay-Ming Teo

13.1 Introduction to Biofouling Management 377

13.2 Polymer Brushes for Surface Functionalization 378

13.3 Biomimetic Anchors for Antifouling Polymer Brushes 379

13.3.1 Mussel Adhesive-Inspired Dopamine Anchors 379

13.3.1.1 Antifouling Polymer Brushes Prepared via the “Grafting-To” Approach on (poly)Dopamine Anchor 383

13.3.1.2 Antifouling Polymer Brushes Prepared via the “Grafting-From” Approach on (poly)Dopamine Anchor 386

13.3.1.3 Direct Grafting of Antifouling Polymer Brushes Containing Anchorable Dopamine-Derived Functionalities 389

13.3.2 (Poly)phenolic Anchors for Antifouling Polymer Brushes 391

13.3.3 Biomolecular Anchors for Antifouling Polymer Brushes 393

13.4 Barnacle Cement as Anchor for Antifouling Polymer Brushes 397

13.5 Conclusion and Outlooks 399

References 400

14 Protein Adsorption Process Based on Molecular Interactions at Well-Defined Polymer Brush Surfaces 405
Sho Sakata, Yuuki Inoue, and Kazuhiko Ishihara

14.1 Introduction 405

14.2 Utility of Polymer Brush Layers as Highly Controllable Polymer Surfaces 406

14.3 Performance of Polymer Brush Surfaces as Antifouling Biointerfaces 408

14.4 Elucidation of Protein Adsorption Based on Molecular Interaction Forces 412

14.5 Concluding Remarks 416

References 417

15 Are Lubricious Polymer Brushes Antifouling? Are Antifouling Polymer Brushes Lubricious? 421
Edmondo M. Benetti and Nicholas D. Spencer

15.1 Introduction 421

15.2 Poly(ethylene glycol) Brushes 422

15.3 Beyond Simple PEG Brushes 424

15.4 Conclusion 429

References 429

16 Biofunctionalized Brush Surfaces for Biomolecular Sensing 433
Shuaidi Zhang and Vladimir V. Tsukruk

16.1 Introduction 433

16.2 Biorecognition Units 435

16.2.1 Antibodies 435

16.2.2 Antibody Fragments 435

16.2.3 Aptamers 437

16.2.4 Peptide Aptamers 438

16.2.5 Enzymes 438

16.2.6 Peptide Nucleic Acid, Lectin, and Molecular Imprinted Polymers 439

16.3 Immobilization Strategy 439

16.3.1 Through Direct Covalent Linkage 440

16.3.1.1 Thiolated Aptamers on Noble Metal 440

16.3.1.2 General Activated Surface Chemistry 442

16.3.1.3 Diels–Alder Cycloaddition 444

16.3.1.4 Staudinger Ligation 444

16.3.1.5 1,3-Dipolar Cycloaddition 446

16.3.2 Through Affinity Tags 447

16.3.2.1 Biotin–Avidin/Streptavidin Pairing 447

16.3.2.2 NTA–Ni2+–Histidine Pairing 448

16.3.2.3 Protein A/Protein G – Fc Pairing 449

16.3.2.4 Oligonucleotide Hybridization 450

16.4 Microstructure and Morphology of Biobrush Layers 451

16.4.1 Grafting Density Control 451

16.4.2 Conformation and Orientation of Recognition Units 453

16.5 Transduction Schemes Based upon Grafted Biomolecules 462

16.5.1 Electrochemical-Based Sensors 462

16.5.2 Field Effect Transistor Based Sensors 463

16.5.3 SPR-Based Sensors 465

16.5.4 Photoluminescence-Based Sensors 466

16.5.5 SERS Sensors 468

16.5.6 Microcantilever Sensors 469

16.6 Conclusions 471

Acknowledgments 472

References 472

17 Phenylboronic Acid and Polymer Brushes: An Attractive Combination with Many Possibilities 479
Solmaz Hajizadeh and Bo Mattiasson

17.1 Introduction: Polymer Brushes and Synthesis 479

17.2 Boronic Acid Brushes 481

17.3 Affinity Separation 483

17.4 Sensors 487

17.5 Biomedical Applications 492

17.6 Conclusions 494

References 494

18 Smart Surfaces Modified with Phenylboronic Acid Containing Polymer Brushes 497
Hongliang Liu, ShutaoWang, and Lei Jiang

18.1 Introduction 497

18.2 Molecular Mechanism of PBA-Based Smart Surfaces 498

18.3 pH-Responsive Surfaces Modified with PBA Polymer Brush and Their Applications 501

18.4 Sugar-Responsive SurfacesModified with PBA Polymer Brush and Their Applications 503

18.5 PBA Polymer Brush–Based pH/Sugar Dual-Responsive OR Logic Gates and Their Applications 504

18.6 PBA Polymer Brush-Based pH/Sugar Dual-Responsive AND Logic Gates and Their Applications 506

18.7 PBA-Based Smart Systems beyond Polymer Brush and Their Applications 509

18.8 Conclusion and Perspective 511

References 512

19 Polymer Brushes andMicroorganisms 515
Madeleine Ramstedt

19.1 Introduction 515

19.1.1 Societal Relevance for Surfaces Interacting with Microbes 515

19.1.2 Microorganisms 516

19.2 Brushes and Microbes 519

19.2.1 Adhesive Surfaces 529

19.2.2 Antifouling Surfaces 530

19.2.2.1 PEG-Based Brushes 531

19.2.2.2 Zwitterionic Brushes 533

19.2.2.3 Brush Density 533

19.2.2.4 Interactive Forces 535

19.2.2.5 Mechanical Interactions 537

19.2.3 Killing Surfaces 537

19.2.3.1 Antimicrobial Peptides 540

19.2.4 Brushes and Fungi 543

19.2.5 Brushes and Algae 546

19.3 Conclusions and Future Perspectives 549

Acknowledgments 551

References 552

20 Design of Polymer Brushes for Cell Culture and Cellular Delivery 557
Danyang Li and Julien E. Gautrot

Abbreviations 557

20.1 Introduction 559

20.2 Protein-Resistant Polymer Brushes for Tissue Engineering and In Vitro Assays 561

20.2.1 Design of Protein-Resistant Polymer Brushes 561

20.2.2 Cell-Resistant Polymer Brushes 565

20.2.3 Patterned Antifouling Brushes for the Development of Cell-Based Assays 567

20.3 Designing Brush Chemistry to Control Cell Adhesion and Proliferation 570

20.3.1 Polyelectrolyte Brushes for Cell Adhesion and Culture 570

20.3.2 Control of Surface Hydrophilicity 573

20.3.3 Surfaces with Controlled Stereochemistry 574

20.3.4 Switchable Brushes Displaying Responsive Behavior for Cell Harvesting and Detachment 576

20.4 Biofunctionalized Polymer Brushes to Regulate Cell Phenotype 581

20.4.1 Protein Coupling to Polymer Brushes to Control Cell Adhesion 581

20.4.2 Peptide-Functionalized Polymer Brushes to Regulate Cell Adhesion, Proliferation, Differentiation, and Migration 583

20.5 Polymer Brushes for Drug and Gene Delivery Applications 586

20.5.1 Polymer Brushes in Drug Delivery 586

20.5.2 Polymer Brushes in Gene Delivery 590

20.6 Summary 593

Acknowledgments 593

References 593

21 DNA Brushes: Self-Assembly, Physicochemical Properties, and Applications 605
Ursula Koniges, Sade Ruffin, and Rastislav Levicky

21.1 Introduction 605

21.2 Applications 605

21.3 Preparation 607

21.4 Physicochemical Properties of DNA Brushes 610

21.5 Hybridization in DNA Brushes 613

21.6 Other Bioprocesses in DNA Brushes 618

21.7 Perspective 619

Acknowledgments 620

References 621

22 DNA Brushes: Advances in Synthesis and Applications 627
Renpeng Gu, Lei Tang, Isao Aritome, and Stefan Zauscher

22.1 Introduction 627

22.2 Synthesis of DNA Brushes 628

22.2.1 Grafting-to Approaches 628

22.2.1.1 Immobilization on Gold Thin Films 628

22.2.1.2 Immobilization on Silicon-Based Substrates 632

22.2.2 Grafting-from Approaches 634

22.2.2.1 Surface-Initiated Enzymatic Polymerization 634

22.2.2.2 Surface-Initiated Rolling Circle Amplification 634

22.2.2.3 Surface-Initiated Hybridization Chain Reaction 634

22.2.3 Synthesis of DNA Brushes on Curved Surfaces 637

22.3 Properties and Applications of DNA Brushes 637

22.3.1 The Effect of DNA-Modifying Enzymes on the DNA Brush Structure 637

22.3.2 Stimulus-Responsive Conformational Changes of DNA Brushes 639

22.3.3 DNA Brush for Cell-Free Surface Protein Expression 643

22.3.4 DNA Brush-Modified Nanoparticles for Biomedical Applications 645

22.4 Conclusion and Outlook 649

References 649

23 Membrane Materials Form Polymer Brush Nanoparticles 655
Erica Green, Emily Fullwood, Julieann Selden, and Ilya Zharov

23.1 Introduction 655

23.2 Colloidal Membranes Pore-Filled with Polymer Brushes 657

23.2.1 Preparation of Silica Colloidal Membranes 657

23.2.2 PAAM Brush-Filled Silica Colloidal Membranes 658

23.2.3 PDMAEMA Brush-Filled Silica Colloidal Membranes 659

23.2.4 PNIPAAM brush-filled silica colloidal membranes 664

23.2.5 Polyalanine Brush-Filled Silica Colloidal Membranes 666

23.2.6 PMMA Brush-Filled SiO2@Au Colloidal Membranes 670

23.2.7 Colloidal Membranes Filled with Polymers Brushes Carrying Chiral Groups 672

23.2.8 pSPM and pSSA Brush-Filled Colloidal Nanopores 673

23.3 Self-Assembled PBNPs Membranes 676

23.3.1 PDMAEMA/PSPM Membranes 676

23.3.2 PHEMA Membranes 678

23.3.3 pSPM and pSSA Membranes 680

23.4 Summary 683

References 683

24 Responsive Polymer Networks and Brushes for Active Plasmonics 687
Nestor Gisbert Quilis, Nityanand Sharma, Stefan Fossati,Wolfgang Knoll, and Jakub Dostalek

24.1 Introduction 687

24.2 Tuning Spectrum of Surface Plasmon Modes 688

24.3 Polymers Used for Actuating of Plasmonic Structures 692

24.3.1 Temperature-Responsive Polymers 692

24.3.2 Optical Stimulus 694

24.3.3 Electrochemical Stimulus 695

24.3.4 Chemical Stimulus 696

24.4 Imprinted Thermoresponsive Hydrogel Nanopillars 697

24.5 Thermoresponsive Hydrogel Nanogratings Fabricated by UV Laser Interference Lithography 699

24.6 Electrochemically Responsive Hydrogel Microgratings Prepared by UV Photolithography 702

24.7 Conclusions 705

Acknowledgments 706

References 706

25 Polymer Brushes as Interfacial Materials for Soft Metal Conductors and Electronics 709
Casey Yan and Zijian Zheng

25.1 Introduction 709

25.2 Mechanisms of Polymer-Assisted Metal Deposition 712

25.3 Role of Polymer Brushes 716

25.4 Selection Criterion of Polymer Brushes Enabling PAMD 716

25.5 Strategies to Fabricate Patterned Metal Conductors 717

25.6 PAMD on Different Substrates and Their Applications in Soft Electronics 720

25.6.1 On Textiles 720

25.6.2 On Plastic Thin films 721

25.6.3 On Elastomers 724

25.6.4 On Sponges 728

25.7 Conclusion, Prospects, and Challenges 731

References 732

26 Nanoarchitectonic Design of Complex Materials Using Polymer Brushes as Structural and Functional Units 735
M. Lorena Cortez, Gisela D´ýaz,Waldemar A. Marmisoll´e, Juan M. Giussi, and Omar Azzaroni

26.1 Introduction 735

26.2 Nanoparticles at Spherical Polymer Brushes: Hierarchical Nanoarchitectonic Construction of Complex Functional Materials 736

26.3 Nanotube and Nanowire Forests Bearing Polymer Brushes 737

26.3.1 Polymer Brushes on Surfaces DisplayingMicrotopographical Hierarchical Arrays 738

26.3.2 Environmentally Responsive Electrospun Nanofibers 740

26.4 Fabrication of Free-Standing “Soft” Micro- and Nanoobjects Using Polymer Brushes 741

26.5 Solid-State Polymer Electrolytes Based on Polymer Brush–Modified Colloidal Crystals 743

26.6 Proton-Conducting Membranes with Enhanced Properties Using Polymer Brushes 745

26.7 Hybrid Architectures Combining Mesoporous Materials and Responsive Polymer Brushes: Gated Molecular Transport Systems and Controlled Delivery Vehicles 747

26.8 Ensembles of Metal NanoparticlesModified with Polymer Brushes 750

26.9 Conclusions 754

Acknowledgments 755

References 755

Index 759