The development of new multi-functional membranes and materials which respond to external stimuli, such as pH, temperature, light, biochemicals or magnetic or electrical signals, represents new approaches to separations, reactions, or recognitions. With multiple cooperative functions, responsive membranes and materials have applications which range from biopharmaceutical, to drug delivery systems to water treatment. Covering recent advances in the generation and application of responsive materials, topics covered include: Development and design of responsive membranes and materials Carbon nanotube membranes Tunable separations, reactions and nanoparticle synthesis Responsive membranes for water treatment Pore-filled membranes for drug release Biologically-inspired responsive materials and hydrogels Biomimetic polymer gels Responsive Membranes and Materials provides a unique, cutting-edge resource for researchers and scientists in membrane science and technology, as well as specialists in separations, biomaterials, bionanotechnology, drug delivery, polymers, and functional 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

List of contributors

Acknowledgements

1 Oligonucleic Acids (“Aptamers”) for Designing Stimuli-Responsive Membranes

1.1 Introduction

1.2 Aptamers – Structure, Function, Incorporation, and Selection

1.3 Characterization Techniques for Aptamer-Target Interactions

1.3.1 Measuring Overall Structural Changes of Aptamers Using QCM - D

1.3.2 Measuring Overall Structural Changes of Aptamers Using DPI

1.4 Aptamers – Applications

1.4.1 Electromechanical Gates

1.4.2 Stimuli-Responsive Nucleic Acid Gates in Nanoparticles

1.4.4 Stimuli-Responsive Aptamer Gates in Nanoparticles

1.4.5 Stimuli-Responsive Aptamer-Based Gating Membranes

1.5 Outlook

Acknowledgements

References

2 Emerging Membrane Nanomaterials – Towards Natural Selection of Functions

2.1 Introduction

2.2 Ion-Pair Conduction Pathways in Liquid and Hybrid Membranes

2.3 Dynamic Insidepore Resolution Towards Emergent Membrane Functions

2.4 Dynameric Membranes and Materials

2.4.1 Constitutional Hybrid Materials

2.4.2 Dynameric Membranes Displaying Tunable Properties on Constitutional Exchange

2.5 Conclusions

Acknowledgement

References

3 Carbon Nanotube Membranes as an Idealized Platform for Protein Channel Mimetic Pumps

3.1 Introduction

3.2 Experimental Understanding of Mass Transport Through CNT s

3.2.1 Ionic Diffusion and Gatekeeper Activity

3.2.2 Gas and Fluid Flow

3.3 Electrostatic Gatekeeping and Electro-osmotic Pumping

3.3.1 Biological Gating

3.4 CNT Membrane Applications

3.5 Conclusions and Future Prospects

Acknowledgements

References

4 Synthesis Aspects in the Design of Responsive Membranes

4.1 Introduction

4.2 Responsive Mechanisms

4.3 Responsive Polymers

4.3.1 Temperature-Responsive Polymers

4.3.2 Polymers that Respond to <hlc>p</hlc> H , Ionic Strength, Light

4.4 Preparation of Responsive Membranes

4.5 Polymer Processing into Membranes

4.5.1 Solvent Casting

4.5.2 Phase Inversion

4.6 In Situ Polymerization

4.6.1 Radiation-Based Methods

4.6.2 Interpenetrating Polymer Networks ( IPN s)

4.7 Surface Modification Using Stimuli-Responsive Polymers

4.8 “Grafting to” Methods

4.8.1 Physical Adsorption – Non-covalent

4.8.2 Chemical Grafting – Covalent

4.8.3 Surface Entrapment – Non-covalent, Physically Entangled

4.9 “Grafting from” – <hlc>a.k.a.</hlc> Surface-Initiated Polymerization

4.9.1 Photo-Initiated Polymerization

4.9.2 Atom Transfer Radical Polymerization

4.9.3 Reversible Addition-Fragmentation Chain Transfer Polymerization

4.9.4 Other Grafting Methods

4.9.5 Summary of “Grafting from” Methods

4.10 Future Directions

References

5 Tunable Separations, Reactions, and Nanoparticle Synthesis in Functionalized Membranes

5.1 Introduction

5.2 Membrane Functionalization

5.2.1 Chemical Modification

5.2.1.1 Periodate Oxidation

5.2.1.2 Epoxy Activation

5.2.1.3 Carbodiimide Coupling

5.2.1.4 Triazine (2,4,6-trichlorotriazine) Activation

5.2.1.5 Substituted Sulfonyl Chloride

5.2.1.6 Carbonylation

5.2.1.7 Silylation of Inorganic (Ceramic) Materials

5.2.1.8 Thiol-Gold Chemistry

5.2.2 Surface Initiated Membrane Modification

5.2.3Cross-Linked Hydrogel (Pore Filled) Membranes

5.2.3.1Temperature Responsive Hydrogels

5.2.3 Layer By Layer Assemblies

5.3 Applications

5.3.1 Water Flux Tunability

5.3.1.1 Modelling the <hlc>p</hlc> H -Responsive Behaviour of Poly(Vinylidene Fluoride) ( PVDF )- PAA Membranes

5.3.2 Tunable Separation of Salts

5.3.2.1 Modelling the Ion Transport Through Polypeptide ( PLGA )-Functionalized Membranes

5.3.3 Charged-Polymer Multilayer Assemblies for Environmental Applications

5.3.3.1 Ultra-High Capacity Metal Capture

5.4 Responsive Membranes and Materials for Catalysis and Reactions

5.4.1 Iron-Functionalized Responsive Membranes

5.4.1.1 Membrane-Immobilized, Iron-Catalysed Free Radical Reactions

5.4.1.2 Tunable F <hlc>e</hlc>0 Nanoparticle Synthesis for Treatment of Contaminated Water

5.4.2 Responsive Membranes for Enzymatic Catalysis

5.4.2.1 Tunable Stacked Membrane Systems

Acknowledgements

References

6 Responsive Membranes for Water Treatment

6.1 Introduction

6.2 Fabrication of Responsive Membranes

6.2.1 Functionalization by Incubation in Liquids

6.2.2 Functionalization by Incorporation of Responsive Groups in the Base Membrane

6.2.3 Surface Modification of Existing Membranes

6.2.3.1 “Grafting to”

6.2.3.2 “Grafting-from”

6.2.3.3 Physical Adsorption, Interfacial Cross-linking, and Pore-Filling

6.3 Outlook

References

7 Functionalization of Polymeric Membranes and Feed Spacers for Fouling Control in Drinking Water Treatment Applications

7.1 Membrane Filtration

7.2 Fouling

7.3 Improving Membrane Performance

7.3.1 Plasma Treatment

7.3.2 Ultraviolet ( UV ) Irradiation

7.3.3 Membrane Modification by Graft Polymerization

7.3.3.1 Free Radical Grafting Reactions

7.3.3.2 Green Chemistry

7.3.3.3 Graft Polymer Examples

7.3.4 Ion Beam Irradiation

7.3.4.1 Ion Beam Induced Property Changes

7.3.4.2 Ion Irradiation of Polymeric Membranes

7.4 Design and Surface Modifications of Feed Spacers for Biofouling Control

7.5 Conclusion

Acknowledgements

References

8 Pore-Filled Membranes As Responsive Release Devices

8.1 Introduction

8.2 Responsive Pore-Filled Membranes

8.3 Development and Characterization of PVDF - PAA Pore-Filled <hlc>p</hlc> H -Sensitive Membranes

8.3.1 Membrane Gel Incorporation (Mass Gain)

8.3.2 Membrane <hlc>p</hlc> H Reversibility

8.3.3 Membrane Water Flux as <hlc>p</hlc> H Varied from 2 to 7.5

8.3.4 Effects of Gel Incorporation on Membrane Pure Water Permeabilities at <hlc>p</hlc> H Neutral and Acidic

8.3.4.1 Membrane Pure Water Permeability

8.3.4.2 Effects of Mass Gain and Cross-Linking Degree at <hlc>p</hlc> H Neutral

8.3.4.3 Effects of Mass Gain and Cross-Linking Degree at <hlc>p</hlc> H Acidic

8.3.4.4 Effects of Mass Gain and Cross-Linking Degree on Valve Ratio

8.3.5 Estimation and Calculation of Pore Size

8.3.5.1 Pore Radius of the Nascent Substrate Membrane

8.3.5.2 Pore Radius of the Pore-Filled Membranes at <hlc>p</hlc> H Acidic

8.3.5.3 Pore Size Estimation and Calculation of the Pore-Filled Membranes at <hlc>p</hlc> H Neutral

8.4 <hlc>p</hlc> H -Sensitive Poly(Vinylidene Fluoride)-Poly(Acrylic Acid) Pore-Filled Membranes for Controlled Drug Release in Ruminant Animals

8.4.1 Determination of Membrane Diffusion Permeability (PS) for Salicylic Acid

8.4.1.1 Determination of the Membrane Diffusion Permeability

8.4.1.2 Effect of the Mass Gain on the Diffusion Permeability at <hlc>p</hlc> H Acidic and <hlc>p</hlc> H Neutral

8.4.1.3 Effect of Mass Gain on the Ratio of the Diffusion Permeability at <hlc>p</hlc> H Acidic to <hlc>p</hlc> H Neutral

8.4.2 Applicability of the Fabricated Pore-Filled Membranes on the Salicylic Acid Release and Retention

References

9 Magnetic Nanocomposites for Remote Controlled Responsive Therapy and in Vivo Tracking

9.1 Introduction

9.1.1 Nanocomposite Polymers

9.1.2 Magnetic Nanoparticles

9.2 Applications of Magnetic Nanocomposite Polymers

9.2.1 Thermal Actuation

9.2.1.1 Swelling

9.2.1.2 Degradation

9.2.1.3 Phase Change

9.2.1.4 Transition Temperature

9.2.2 Thermal Therapy

9.2.3 Mechanical Actuation

9.2.3.1 Controlled Drug Release

9.2.3.2 Mechanical Actuators for Therapeutic Applications

9.2.4 In Vivo Tracking and Applications

9.3 Concluding Remarks

References

10 The Interactions between Salt Ions and Thermo-Responsive Poly ( N -Isopropylacrylamide) from Molecular Dynamics Simulations

10.1 Introduction

10.2 Computational Details

10.3 Results and Discussion

10.4 Conclusion

Acknowledgement

References

11 Biologically-Inspired Responsive Materials: Integrating Biological Function into Synthetic Materials

11.2 Introduction

11.2 Biomimetics in Biotechnology

11.3 Hinge-Motion Binding Proteins

11.4 Calmodulin

11.5 Biologically-Inspired Responsive Membranes

11.7 Stimuli-Responsive Hydrogels

11.7 Micro/Nanofabrication of Hydrogels

11.8 Mechanical Characterization of Hydrogels

11.9 Creep Properties of Hydrogels

11.10 Conclusions and Future Perspectives

Acknowledgements

References

12. Responsive Colloids with Controlled Topology

12.1 Introduction

12.2 Inert Core/Responsive Shell Particles

12.3 Responsive Core/Responsive Shell Particles

12.4 Hollow Particles

12.5 Janus Particles

12.6 Summary

References

13 Novel Biomimetic Polymer Gels Exhibiting Self-Oscillation

13.1 Introduction

13.2 The Design Concept of Self-Oscillating Gel

13.3 Aspects of the Autonomous Swelling–Deswelling Oscillation Design of Biomimetic Actuator Using Self-Oscillating Polymer and Gel

13.4.1 Ciliary Motion Actuator (Artificial Cilia)

13.4.2 Self-Walking Gel

13.4.3 Theoretical Simulation of the Self-Oscillating Gel

13.5 Mass Transport Surface Utilizing Peristaltic Motion of Gel

13.6 Self-Oscillating Polymer Chains and Microgels as “Nanooscillators”

13.6.1 Solubility Oscillation of Polymer Chains

13.6.2 Self-Flocculating/Dispersing Oscillation of Microgels

13.6.3 Viscosity Oscillation of Polymer Solution and Microgel Dispersion

13.6.4 Attempts of Self-Oscillation under Acid- and Oxidant-Free Physiological Conditions

13.7 Conclusion

References

14 Electroactive Polymer Soft Material Based on Dielectric Elastomer

14.1 Introduction to Electroactive Polymers

14.1.1 Development History

14.1.2 Classification

14.1.3 Electronic Electroactive Polymers

14.1.3.1 Dielectric Elastomers

14.1.3.2 Electrostrictive Graft Elastomers

14.1.3.3 Ferroelectric Polymers

14.1.3.4 Electro-Viscoelastic Elastomers

14.1.4 Ionic Electroactive Polymers

14.1.4.1 Carbon Nanotubes

14.1.4.2 Ionic Polymer Gels

14.1.4.3 Electrorheological Fluids

14.1.5 Electroactive Polymer Applications

14.1.6 Application of Dielectric Elastomers

14.1.6.1 Walking Robot

14.1.6.2 Energy-Harvesting Device

14.1.6.3 Micro Unmanned Aerial Vehicles

14.1.6.4 Clamping Device Using Ionic Polymer–Metal Composites

14.1.6.5 Anti-Gravity Service Using Conductive Polymers

14.1.6.6 Facial Expression

14.1.6.7 Braille Tactual Displays

14.1.6.8 Loudspeaker

14.1.7 Manufacturing the Main Structure of Actuators Using EAP Materials

14.1.7.1 Stacked Structure and the Helical Structure

14.1.7.2 The Folding Structure

14.1.7.3 The Round-Hole Structure

14.1.8 The Current Problem for EAP Materials and their Prospects

14.2 Materials of Dielectric Elastomers

14.2.1 The Working Principle of Dielectric Elastomers

14.2.2 Material Modification of Dielectric Elastomer

14.2.2.1 Introduction of Dielectric Elastomer Materials

14.2.2.2 Impact of Pre-Stretching on Dielectric Elastomer Material

14.2.3 Dielectric Elastomer Composite

14.2.3.1 Particle-Filled Dielectric Elastomer Composite

14.2.3.2 Dielectric Elastomer of Interpenetrating Polymer Network ( IPN )

14.3 The Theory of Dielectric Elastomers

14.3.1 Free Energy of Dielectric Elastomer Electromechanical Coupling System

14.3.2 Special Elastic Energy

14.3.3 Special Electric Field Energy

14.3.4 Incompressible Dielectric Elastomer

14.3.5 Model of Several Dielectric Elastomers

14.3.5.1 Model of Ideal Dielectric Elastomers

14.3.5.2 Model of Electrostriction Dielectric Elastomers

14.3.5.3 Model of Dielectric Elastomer of Interpenetrating Polymer Networks ( IPN <hlc>s</hlc>)

14.3.5.4 Model of Strain-Hardening Dielectric Elastomer

14.3.5.5 Model of Polarization Saturation Dielectric Elastomer

14.3.5.6 Model of Dielectric Elastomer Composite Material

14.3.5.7 Model of Thermal Dielectric Elastomer Material

14.3.5.8 Model of Viscoelasticity Dielectric Elastomer

14.4 Failure Model of a Dielectric Elastomer

14.4.1 Electrical Breakdown

14.4.2 Electromechanical Instability and Snap-Through Instability

14.4.3 Loss of Tension

14.4.4 Rupture by Stretching

14.4.5 Zero Electric Field Condition

14.4.6 Super-Electrostriction Deformation of a Dielectric Elastomer

14.5 Converter Theory of Dielectric Elastomer

14.5.1 Principle for Conversion Cycle

14.5.2 Plane Actuator

14.5.3 Spring-Roll Dielectric Elastomer Actuator

14.5.4 Tube-Type Actuator

14.5.5 Film-Spring System

14.5.6 Energy Harvester

14.5.7 The Non-linear Vibration of a Dielectric Elastomer Ball

14.5.8 Folded Actuator

References

15 Responsive Membrane/Material-Based Separations: Research and Development Needs

15.1 Introduction

15.2 Water Treatment

15.3 Biological Applications

15.4 Gas Separation and Additional Applications

References

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