Responsive Membranes and Materials

Dibakar Bhattacharyya is the University of Kentucky Alumni Professor of Chemical Engineering and a Fellow of the AIChE. He received his Ph.D. from the Illinois Institute of Technology, M.S. from Northwestern University, and B.S. from Jadavpur University. He is the Co-Founder of the Center for Membrane Sciences at the University of Kentucky. He has published over 180 refereed journal articles and book chapters, and five U.S. Patents. At the Dr. Bhattacharyya was honored for his contributions in the area of Functionalized Membranes at the 2007 NAMS Annual Meeting, and he was the main plenary speaker at the SIMPAM 2009 Membrane Conference in Brazil.Sylvia Daunert is the Gill Eminent Professor of Analytical and Biological Chemistry at the University of Kentucky. Her research is in the area of Bioanalytical Chemistry, at the interface between Analytical Chemistry, Molecular Biology, and Bioengineering.Ranil Wickramasinghe is Professor at Colorado State University. His research focuses on the development of membranes and membrane separation processes for bioseparations, water treatment and biofuels applications.Thomas Schäfer is Ikerbasque Research Professor at the Institute of Polymer Materials (POLYMAT) of the University of the Basque Country in San Sebastián, Spain.

• Preface xvList of Contributors xxi1 Oligonucleic Acids (“Aptamers”) for Designing Stimuli-Responsive Membranes 1Veli Cengiz O¨ zalp, Mar´ýa Bele´n Serrano-Santos and Thomas Scha¨fer1.1 Introduction 11.2 Aptamers – Structure, Function, Incorporation, and Selection 41.3 Characterization Techniques for Aptamer-Target Interactions 71.3.1 Measuring Overall Structural Changes of Aptamers Using QCM-D 81.3.2 Measuring Overall Structural Changes of Aptamers Using DPI 131.4 Aptamers – Applications 171.4.1 Electromechanical Gates 171.4.2 Stimuli-Responsive Nucleic Acid Gates in Nanoparticles 171.4.3 Stimuli-Responsive Aptamer Gates in Nanoparticles 201.4.4 Stimuli-Responsive Aptamer-Based Gating Membranes 221.5 Outlook 25Acknowledgements 26References 262 Emerging Membrane Nanomaterials – Towards Natural Selection of Functions 31Mihail Barboiu2.1 Introduction 312.2 Ion-Pair Conduction Pathways in Liquid and Hybrid Membranes 322.3 Dynamic Insidepore Resolution Towards Emergent Membrane Functions 362.4 Dynameric Membranes and Materials 392.4.1 Constitutional Hybrid Materials 392.4.2 Dynameric Membranes Displaying Tunable Properties on Constitutional Exchange 412.5 Conclusion 46Acknowledgements 47References 473 Carbon Nanotube Membranes as an Idealized Platform for Protein Channel Mimetic Pumps 51Bruce Hinds3.1 Introduction 513.2 Experimental Understanding of Mass Transport Through CNTs 563.2.1 Ionic Diffusion and Gatekeeper Activity 573.2.2 Gas and Fluid Flow 573.3 Electrostatic Gatekeeping and Electro-osmotic Pumping 593.3.1 Biological Gating 623.4 CNT Membrane Applications 633.5 Conclusion and Future Prospects 66Acknowledgements 67References 674 Synthesis Aspects in the Design of Responsive Membranes 73Scott M. Husson4.1 Introduction 734.2 Responsive Mechanisms 744.3 Responsive Polymers 754.3.1 Temperature-Responsive Polymers 754.3.2 Polymers that Respond to pH, Ionic Strength, Light 764.4 Preparation of Responsive Membranes 774.5 Polymer Processing into Membranes 784.5.1 Solvent Casting 784.5.2 Phase Inversion 784.6 In Situ Polymerization 784.6.1 Radiation-Based Methods 784.6.2 Interpenetrating Polymer Networks (IPNs) 794.7 Surface Modification Using Stimuli-Responsive Polymers 794.8 “Grafting to” Methods 814.8.1 Physical Adsorption – Non-covalent 814.8.2 Chemical Grafting – Covalent 814.8.3 Surface Entrapment – Non-covalent, Physically Entangled 824.9 “Grafting from” – a.k.a. Surface-Initiated Polymerization 834.9.1 Photo-Initiated Polymerization 834.9.2 Atom Transfer Radical Polymerization 854.9.3 Reversible Addition-Fragmentation Chain Transfer Polymerization 874.9.4 Other Grafting Methods 914.9.5 Summary of “Grafting from” Methods 914.10 Future Directions 91References 925 Tunable Separations, Reactions, and Nanoparticle Synthesis in Functionalized Membranes 97Scott R. Lewis, Vasile Smuleac, Li Xiao and D. Bhattacharyya5.1 Introduction 975.2 Membrane Functionalization 985.2.1 Chemical Modification 985.2.2 Surface Initiated Membrane Modification 1015.2.3 Cross-Linked Hydrogel (Pore Filled) Membranes 1025.2.4 Layer by Layer Assemblies 1035.3 Applications 1045.3.1 Water Flux Tunability 1045.3.2 Tunable Separation of Salts 1095.3.3 Charged-Polymer Multilayer Assemblies for Environmental Applications 1135.4 Responsive Membranes and Materials for Catalysis and Reactions 1155.4.1 Iron-Functionalized Responsive Membranes 1165.4.2 Responsive Membranes for Enzymatic Catalysis 127Acknowledgements 132References 1326 Responsive Membranes for Water Treatment 143Qian Yang and S. R. Wickramasinghe6.1 Introduction 1436.2 Fabrication of Responsive Membranes 1446.2.1 Functionalization by Incubation in Liquids 1456.2.2 Functionalization by Incorporation of Responsive Groups in the Base Membrane 1456.2.3 Surface Modification of Existing Membranes 1486.3 Outlook 158References 1597 Functionalization of Polymeric Membranes and Feed Spacers for Fouling Control in Drinking Water Treatment Applications 163Colleen Gorey, Richard Hausman and Isabel C. Escobar7.1 Membrane Filtration 1637.2 Fouling 1657.3 Improving Membrane Performance 1687.3.1 Plasma Treatment 1687.3.2 Ultraviolet (UV) Irradiation 1707.3.3 Membrane Modification by Graft Polymerization 1717.3.4 Ion Beam Irradiation 1767.4 Design and Surface Modifications of Feed Spacers for Biofouling Control 1787.5 Conclusion 180Acknowledgements 181References 1818 Pore-Filled Membranes as Responsive Release Devices 187Kang Hu and James Dickson8.1 Introduction 1878.2 Responsive Pore-Filled Membranes 1888.3 Development and Characterization of PVDF-PAA Pore-Filled pH-Sensitive Membranes 1908.3.1 Membrane Gel Incorporation (Mass Gain) 1918.3.2 Membrane pH Reversibility 1918.3.3 Membrane Water Flux as pH Varied from 2 to 7.5 1918.3.4 Effects of Gel Incorporation on Membrane Pure Water Permeabilities at pH Neutral and Acidic 1958.3.5 Estimation and Calculation of Pore Size 1988.4 pH-Sensitive Poly(Vinylidene Fluoride)-Poly(Acrylic Acid) Pore-Filled Membranes for Controlled Drug Release in Ruminant Animals 2018.4.1 Determination of Membrane Diffusion Permeability (PS) for Salicylic Acid 2028.4.2 Applicability of the Fabricated Pore-Filled Membranes on the Salicylic Acid Release and Retention 205References 2079 Magnetic Nanocomposites for Remote Controlled Responsive Therapy and in Vivo Tracking 211Ashley M. Hawkins, David A. Puleo and J. Zach Hilt9.1 Introduction 2119.1.1 Nanocomposite Polymers 2119.1.2 Magnetic Nanoparticles 2129.2 Applications of Magnetic Nanocomposite Polymers 2129.2.1 Thermal Actuation 2139.2.2 Thermal Therapy 2189.2.3 Mechanical Actuation 2209.2.4 In Vivo Tracking and Applications 2249.3 Concluding Remarks 224References 22410 The Interactions between Salt Ions and Thermo-Responsive Poly (N-Isopropylacrylamide) from Molecular Dynamics Simulations 229Hongbo Du and Xianghong Qian10.1 Introduction 22910.2 Computational Details 23010.3 Results and Discussion 23210.4 Conclusion 238Acknowledgements 240References 24011 Biologically-Inspired Responsive Materials: Integrating Biological Function into Synthetic Materials 243Kendrick Turner, Santosh Khatwani and Sylvia Daunert11.1 Introduction 24311.2 Biomimetics in Biotechnology 24511.3 Hinge-Motion Binding Proteins 24911.4 Calmodulin 25011.5 Biologically-Inspired Responsive Membranes 25111.6 Stimuli-Responsive Hydrogels 25311.7 Micro/Nanofabrication of Hydrogels 25511.8 Mechanical Characterization of Hydrogels 25611.9 Creep Properties of Hydrogels 25711.10 Conclusion and Future Perspectives 258Acknowledgements 258References 25812 Responsive Colloids with Controlled Topology 269Jeffrey C. Gaulding, Emily S. Herman and L. Andrew Lyon12.1 Introduction 26912.2 Inert Core/Responsive Shell Particles 27012.3 Responsive Core/Responsive Shell Particles 27512.4 Hollow Particles 28112.5 Janus Particles 28612.6 Summary 292References 29313 Novel Biomimetic Polymer Gels Exhibiting Self-Oscillation 301Ryo Yoshida13.1 Introduction 30113.2 The Design Concept of Self-Oscillating Gel 30313.3 Aspects of the Autonomous Swelling–Deswelling Oscillation 30313.4 Design of Biomimetic Actuator Using Self-Oscillating Polymer and Gel 30613.4.1 Ciliary Motion Actuator (Artificial Cilia) 30613.4.2 Self-Walking Gel 30713.4.3 Theoretical Simulation of the Self-Oscillating Gel 30713.5 Mass Transport Surface Utilizing Peristaltic Motion of Gel 30813.6 Self-Oscillating Polymer Chains and Microgels as “Nanooscillators” 30913.6.1 Solubility Oscillation of Polymer Chains 30913.6.2 Self-Flocculating/Dispersing Oscillation of Microgels 31013.6.3 Viscosity Oscillation of Polymer Solution and Microgel Dispersion 31113.6.4 Attempts of Self-Oscillation under Acid- and Oxidant-Free Physiological Conditions 31113.7 Conclusion 312References 31214 Electroactive Polymer Soft Material Based on Dielectric Elastomer 315Liwu Liu, Zhen Zhang, Yanju Liu and Jinsong Leng14.1 Introduction to Electroactive Polymers 31514.1.1 Development History 31614.1.2 Classification 31614.1.3 Electronic Electroactive Polymers 31614.1.4 Ionic Electroactive Polymers 31814.1.5 Electroactive Polymer Applications 31814.1.6 Application of Dielectric Elastomers 31814.1.7 Manufacturing the Main Structure of Actuators Using EAP Materials 32714.1.8 The Current Problem for EAP Materials and their Prospects 32914.2 Materials of Dielectric Elastomers 33014.2.1 The Working Principle of Dielectric Elastomers 33014.2.2 Material Modification of Dielectric Elastomer 33114.2.3 Dielectric Elastomer Composite 33414.3 The Theory of Dielectric Elastomers 33614.3.1 Free Energy of Dielectric Elastomer Electromechanical Coupling System 33614.3.2 Special Elastic Energy 33914.3.3 Special Electric Field Energy 34114.3.4 Incompressible Dielectric Elastomer 34214.3.5 Model of Several Dielectric Elastomers 34214.4 Failure Model of a Dielectric Elastomer 35614.4.1 Electrical Breakdown 35714.4.2 Electromechanical Instability and Snap-Through Instability 35714.4.3 Loss of Tension 35814.4.4 Rupture by Stretching 35914.4.5 Zero Electric Field Condition 35914.4.6 Super-Electrostriction Deformation of a Dielectric Elastomer 35914.5 Converter Theory of Dielectric Elastomer 36114.5.1 Principle for Conversion Cycle 36114.5.2 Plane Actuator 36214.5.3 Spring-Roll Dielectric Elastomer Actuator 36414.5.4 Tube-Type Actuator 36514.5.5 Film-Spring System 36914.5.6 Energy Harvester 37214.5.7 The Non-Linear Vibration of a Dielectric Elastomer Ball 37614.5.8 Folded Actuator 377References 37915 Responsive Membranes/Material-Based Separations: Research and Development Needs 385Rosemarie D. Wesson, Elizabeth S. Dow and Sonya R. Williams15.1 Introduction 38515.2 Water Treatment 38615.3 Biological Applications 38715.4 Gas Separation and Additional Applications 388References 389Index 395

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