Serves as a guide for seasoned researchers and students alike, who wish to learn about the cross-fertilization between biology and materials that is driving this emerging area of science
This book covers the most relevant topics in basic research and those having potential technological applications for the field of biopolymer brushes. This area has experienced remarkable increase in development of practical applications in nanotechnology and biotechnology over the past decade. In view of the rapidly growing activity and interest in the field, this book covers the introductory features of polymer brushes and presents a unifying and stimulating overview of the theoretical aspects and emerging applications. It immerses readers in the historical perspective and the frontiers of research where our knowledge is increasing steadily - providing them with a feeling of the enormous potential, the multiple applications, and the many up-and-coming trends behind the development of macromolecular interfaces based on the use of polymer brushes.
Polymer and Biopolymer Brushes: Fundamentals and Applications in Materials offers chapters on: Functionalization of Surfaces Using Polymer Brushes; Polymer Brushes by ATRP and Surface-Mediated RAFT Polymerization for Biological Functions; Electro-Induced Copper Catalyzed Surface Modification with Monolayer and Polymer Brush; Polymer Brushes on Flat and Curved Substrates; Biomimetic Anchors for Antifouling Polymer Brush Coating; Glycopolymer Brushes Presenting Sugars in Their Natural Form; Smart Surfaces Modified with Phenylboronic Acid-Containing Polymer Brushes; DNA Brushes; Polymer Brushes as Interfacial Materials for Soft Metal Conductors and Electronics; and more.
- Presents a comprehensive theory/simulation section that will be valuable for all readers
- Includes chapters not only on the biological applications of polymer brushes but also on biological systems that resemble polymer brushes on flat surfaces
- Addresses applications in coatings, friction, sensors, microelectromechanical systems, and biomaterials
- Devotes particular attention to the functional aspects of hybrid nanomaterials employing polymer brushes as functional units
Polymer and Biopolymer Brushes: Fundamentals and Applications in Materials is aimed at both graduate students and researchers new to this subject as well as scientists already engaged in the study and development of polymer brushes.
Table of Contents
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´Ã½az,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
