Preface xv
List of Contributors xxi
1 Oligonucleic Acids ("Aptamers") for Designing Stimuli-Responsive Membranes 1
Veli Cengiz O¿ zalp, Mar¿ýa Bele¿n Serrano-Santos and Thomas Schäfer
1.1 Introduction 1
1.2 Aptamers - Structure, Function, Incorporation, and Selection 4
1.3 Characterization Techniques for Aptamer-Target Interactions 7
1.3.1 Measuring Overall Structural Changes of Aptamers Using QCM-D 8
1.3.2 Measuring Overall Structural Changes of Aptamers Using DPI 13
1.4 Aptamers - Applications 17
1.4.1 Electromechanical Gates 17
1.4.2 Stimuli-Responsive Nucleic Acid Gates in Nanoparticles 17
1.4.3 Stimuli-Responsive Aptamer Gates in Nanoparticles 20
1.4.4 Stimuli-Responsive Aptamer-Based Gating Membranes 22
1.5 Outlook 25
Acknowledgements 26
References 26
2 Emerging Membrane Nanomaterials - Towards Natural Selection of Functions 31
Mihail Barboiu
2.1 Introduction 31
2.2 Ion-Pair Conduction Pathways in Liquid and Hybrid Membranes 32
2.3 Dynamic Insidepore Resolution Towards Emergent Membrane Functions 36
2.4 Dynameric Membranes and Materials 39
2.4.1 Constitutional Hybrid Materials 39
2.4.2 Dynameric Membranes Displaying Tunable Properties on Constitutional Exchange 41
2.5 Conclusion 46
Acknowledgements 47
References 47
3 Carbon Nanotube Membranes as an Idealized Platform for Protein Channel Mimetic Pumps 51
Bruce Hinds
3.1 Introduction 51
3.2 Experimental Understanding of Mass Transport Through CNTs 56
3.2.1 Ionic Diffusion and Gatekeeper Activity 57
3.2.2 Gas and Fluid Flow 57
3.3 Electrostatic Gatekeeping and Electro-osmotic Pumping 59
3.3.1 Biological Gating 62
3.4 CNT Membrane Applications 63
3.5 Conclusion and Future Prospects 66
Acknowledgements 67
References 67
4 Synthesis Aspects in the Design of Responsive Membranes 73
Scott M. Husson
4.1 Introduction 73
4.2 Responsive Mechanisms 74
4.3 Responsive Polymers 75
4.3.1 Temperature-Responsive Polymers 75
4.3.2 Polymers that Respond to pH, Ionic Strength, Light 76
4.4 Preparation of Responsive Membranes 77
4.5 Polymer Processing into Membranes 78
4.5.1 Solvent Casting 78
4.5.2 Phase Inversion 78
4.6 In Situ Polymerization 78
4.6.1 Radiation-Based Methods 78
4.6.2 Interpenetrating Polymer Networks (IPNs) 79
4.7 Surface Modification Using Stimuli-Responsive Polymers 79
4.8 "Grafting to" Methods 81
4.8.1 Physical Adsorption - Non-covalent 81
4.8.2 Chemical Grafting - Covalent 81
4.8.3 Surface Entrapment - Non-covalent, Physically Entangled 82
4.9 "Grafting from" - a.k.a. Surface-Initiated Polymerization 83
4.9.1 Photo-Initiated Polymerization 83
4.9.2 Atom Transfer Radical Polymerization 85
4.9.3 Reversible Addition-Fragmentation Chain Transfer Polymerization 87
4.9.4 Other Grafting Methods 91
4.9.5 Summary of "Grafting from" Methods 91
4.10 Future Directions 91
References 92
5 Tunable Separations, Reactions, and Nanoparticle Synthesis in Functionalized Membranes 97
Scott R. Lewis, Vasile Smuleac, Li Xiao and D. Bhattacharyya
5.1 Introduction 97
5.2 Membrane Functionalization 98
5.2.1 Chemical Modification 98
5.2.2 Surface Initiated Membrane Modification 101
5.2.3 Cross-Linked Hydrogel (Pore Filled) Membranes 102
5.2.4 Layer by Layer Assemblies 103
5.3 Applications 104
5.3.1 Water Flux Tunability 104
5.3.2 Tunable Separation of Salts 109
5.3.3 Charged-Polymer Multilayer Assemblies for Environmental Applications 113
5.4 Responsive Membranes and Materials for Catalysis and Reactions 115
5.4.1 Iron-Functionalized Responsive Membranes 116
5.4.2 Responsive Membranes for Enzymatic Catalysis 127
Acknowledgements 132
References 132
6 Responsive Membranes for Water Treatment 143
Qian Yang and S. R. Wickramasinghe
6.1 Introduction 143
6.2 Fabrication of Responsive Membranes 144
6.2.1 Functionalization by Incubation in Liquids 145
6.2.2 Functionalization by Incorporation of Responsive Groups in the Base Membrane 145
6.2.3 Surface Modification of Existing Membranes 148
6.3 Outlook 158
References 159
7 Functionalization of Polymeric Membranes and Feed Spacers for Fouling Control in Drinking Water Treatment Applications 163
Colleen Gorey, Richard Hausman and Isabel C. Escobar
7.1 Membrane Filtration 163
7.2 Fouling 165
7.3 Improving Membrane Performance 168
7.3.1 Plasma Treatment 168
7.3.2 Ultraviolet (UV) Irradiation 170
7.3.3 Membrane Modification by Graft Polymerization 171
7.3.4 Ion Beam Irradiation 176
7.4 Design and Surface Modifications of Feed Spacers for Biofouling Control 178
7.5 Conclusion 180
Acknowledgements 181
References 181
8 Pore-Filled Membranes as Responsive Release Devices 187
Kang Hu and James Dickson
8.1 Introduction 187
8.2 Responsive Pore-Filled Membranes 188
8.3 Development and Characterization of PVDF-PAA Pore-Filled pH-Sensitive Membranes 190
8.3.1 Membrane Gel Incorporation (Mass Gain) 191
8.3.2 Membrane pH Reversibility 191
8.3.3 Membrane Water Flux as pH Varied from 2 to 7.5 191
8.3.4 Effects of Gel Incorporation on Membrane Pure Water Permeabilities at pH Neutral and Acidic 195
8.3.5 Estimation and Calculation of Pore Size 198
8.4 pH-Sensitive Poly(Vinylidene Fluoride)-Poly(Acrylic Acid) Pore-Filled Membranes for Controlled Drug Release in Ruminant Animals 201
8.4.1 Determination of Membrane Diffusion Permeability (PS) for Salicylic Acid 202
8.4.2 Applicability of the Fabricated Pore-Filled Membranes on the Salicylic Acid Release and Retention 205
References 207
9 Magnetic Nanocomposites for Remote Controlled Responsive Therapy and in Vivo Tracking 211
Ashley M. Hawkins, David A. Puleo and J. Zach Hilt
9.1 Introduction 211
9.1.1 Nanocomposite Polymers 211
9.1.2 Magnetic Nanoparticles 212
9.2 Applications of Magnetic Nanocomposite Polymers 212
9.2.1 Thermal Actuation 213
9.2.2 Thermal Therapy 218
9.2.3 Mechanical Actuation 220
9.2.4 In Vivo Tracking and Applications 224
9.3 Concluding Remarks 224
References 224
10 The Interactions between Salt Ions and Thermo-Responsive Poly (N-Isopropylacrylamide) from Molecular Dynamics Simulations 229
Hongbo Du and Xianghong Qian
10.1 Introduction 229
10.2 Computational Details 230
10.3 Results and Discussion 232
10.4 Conclusion 238
Acknowledgements 240
References 240
11 Biologically-Inspired Responsive Materials: Integrating Biological Function into Synthetic Materials 243
Kendrick Turner, Santosh Khatwani and Sylvia Daunert
11.1 Introduction 243
11.2 Biomimetics in Biotechnology 245
11.3 Hinge-Motion Binding Proteins 249
11.4 Calmodulin 250
11.5 Biologically-Inspired Responsive Membranes 251
11.6 Stimuli-Responsive Hydrogels 253
11.7 Micro/Nanofabrication of Hydrogels 255
11.8 Mechanical Characterization of Hydrogels 256
11.9 Creep Properties of Hydrogels 257
11.10 Conclusion and Future Perspectives 258
Acknowledgements 258
References 258
12 Responsive Colloids with Controlled Topology 269
Jeffrey C. Gaulding, Emily S. Herman and L. Andrew Lyon
12.1 Introduction 269
12.2 Inert Core/Responsive Shell Particles 270
12.3 Responsive Core/Responsive Shell Particles 275
12.4 Hollow Particles 281
12.5 Janus Particles 286
12.6 Summary 292
References 293
13 Novel Biomimetic Polymer Gels Exhibiting Self-Oscillation 301
Ryo Yoshida
13.1 Introduction 301
13.2 The Design Concept of Self-Oscillating Gel 303
13.3 Aspects of the Autonomous Swelling-Deswelling Oscillation 303
13.4 Design of Biomimetic Actuator Using Self-Oscillating Polymer and Gel 306
13.4.1 Ciliary Motion Actuator (Artificial Cilia) 306
13.4.2 Self-Walking Gel 307
13.4.3 Theoretical Simulation of the Self-Oscillating Gel 307
13.5 Mass Transport Surface Utilizing Peristaltic Motion of Gel 308
13.6 Self-Oscillating Polymer Chains and Microgels as "Nanooscillators" 309
13.6.1 Solubility Oscillation of Polymer Chains 309
13.6.2 Self-Flocculating/Dispersing Oscillation of Microgels 310
13.6.3 Viscosity Oscillation of Polymer Solution and Microgel Dispersion 311
13.6.4 Attempts of Self-Oscillation under Acid- and Oxidant-Free Physiological Conditions 311
13.7 Conclusion 312
References 312
14 Electroactive Polymer Soft Material Based on Dielectric Elastomer 315
Liwu Liu, Zhen Zhang, Yanju Liu and Jinsong Leng
14.1 Introduction to Electroactive Polymers 315
14.1.1 Development History 316
14.1.2 Classification 316
14.1.3 Electronic Electroactive Polymers 316
14.1.4 Ionic Electroactive Polymers 318
14.1.5 Electroactive Polymer Applications 318
14.1.6 Application of Dielectric Elastomers 318
14.1.7 Manufacturing the Main Structure of Actuators Using EAP Materials 327
14.1.8 The Current Problem for EAP Materials and their Prospects 329
14.2 Materials of Dielectric Elastomers 330
14.2.1 The Working Principle of Dielectric Elastomers 330
14.2.2 Material Modification of Dielectric Elastomer 331
14.2.3 Dielectric Elastomer Composite 334
14.3 The Theory of Dielectric Elastomers 336
14.3.1 Free Energy of Dielectric Elastomer Electromechanical Coupling System 336
14.3.2 Special Elastic Energy 339
14.3.3 Special Electric Field Energy 341
14.3.4 Incompressible Dielectric Elastomer 342
14.3.5 Model of Several Dielectric Elastomers 342
14.4 Failure Model of a Dielectric Elastomer 356
14.4.1 Electrical Breakdown 357
14.4.2 Electromechanical Instability and Snap-Through Instability 357
14.4.3 Loss of Tension 358
14.4.4 Rupture by Stretching 359
14.4.5 Zero Electric Field Condition 359
14.4.6 Super-Electrostriction Deformation of a Dielectric Elastomer 359
14.5 Converter Theory of Dielectric Elastomer 361
14.5.1 Principle for Conversion Cycle 361
14.5.2 Plane Actuator 362
14.5.3 Spring-Roll Dielectric Elastomer Actuator 364
14.5.4 Tube-Type Actuator 365
14.5.5 Film-Spring System 369
14.5.6 Energy Harvester 372
14.5.7 The Non-Linear Vibration of a Dielectric Elastomer Ball 376
14.5.8 Folded Actuator 377
References 379
15 Responsive Membranes/Material-Based Separations: Research and Development Needs 385
Rosemarie D. Wesson, Elizabeth S. Dow and Sonya R. Williams
15.1 Introduction 385
15.2 Water Treatment 386
15.3 Biological Applications 387
15.4 Gas Separation and Additional Applications 388
References 389
Index 395
