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Beschreibung

This book addresses the reader to use synergistically the concepts of membranes and sensors materials. It contains insightful contributions from leading scientists working in both the fields. The focus is on the fabrication of smart membranes from sensor materials and related impact on many technologically sophisticated areas such as telemedicine, microfluidics, drug delivery targeting, (bio)separation, labs-on-a-chip, textiles, power storage and release, environment monitoring, agro-food safety, cosmetics, architecture, automotive and so on. This book covers various topics, including the choice of materials and techniques for assembling responsive membranes with ability to transport mass, energy and signals on demand; the reader will find through the book an extensive description of the best techniques used to monitor molecular scale events, which are regarded as responsible for the smartness of multifunctional objects and for the conversion of chemical signals into optical, electrical, thermal and mechanical responses. The reader is encouraged to use this cross-disciplinary discussion for his own research. Chemical, biological and physical concepts, expressed through the book, contribute to form a common language, which will allow the reader to discover causes for reflection and innovation, measuring how smart objects with desired properties can be tailored from exiting materials and used flexibly for different developed applications. Specifically: * This book deals with materials smartness and suitable techniques to assemble and characterize them in sensor-like membranes. * This book shows how ultra-smart functional devices can be accomplished by using traditional raw materials. * This book describes particular key events, which control 'sense to react and adapt' mechanisms. The potential of sensor-like membranes in some key strategic fields is examined with particular emphasis on biomedicine, food and textiles markets. The benefits arising from the use of smart membranes are analysed in terms of life quality, safety, and innovation.

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Veröffentlichungsjahr: 2014

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Contents

Cover

Half Title page

Title page

Copyright page

Dedication

Preface

Part 1: Sensing Materials for Smart Membranes

Chapter 1: Interfaces Based on Carbon Nanotubes, Ionic Liquids and Polymer Matrices for Sensing and Membrane Separation Applications

1.1 Introduction

1.2 Ionic Liquid-Carbon Nanotubes Composites for Sensing Interfaces

1.3 Ionic Liquid Interfaces for Detection and Separation of Gases and Solvents

1.4 Ionic Liquid-Polymer Interfaces for Membrane Separation Processes

1.5 Conclusions

Acknowledgement

References

Chapter 2: Photo-Responsive Hydrogels for Adaptive Membranes

2.1 Introduction

2.2 Photo-Responsive Hydrogel Membranes

2.3 Photo-Thermally Responsive Hydrogel Membranes

2.4 Summary

2.5 Acknowledgements

Abbreviations

References

Chapter 3: Smart Vesicles: Synthesis, Characterization and Applications

3.1 Introduction

3.2 Synthesis of Soft Vesicles

3.3 Synthesis of Hard Vesicles

3.4 Characterization of Vesicular Structures

3.5 Stimuli–Responsive Behaviors of Vesicular Structures

3.6 Application of Vesicles

3.7 Conclusions

Acknowledgment

References

Part 2: Stimuli-Responsive Interfaces

Chapter 4: Computational Modeling of Sensing Membranes and Supramolecular Interactions

4.1 Introduction

4.2 Non-covalent Interactions: A Physical and a Chemical View

4.3 Physical Interactions

4.4 Chemical Interactions

4.5 Computational Methods for Supramolecular Interactions

4.6 Classical Force Fields

4.7 Conclusions

Acknowledgement

References

Chapter 5: Sensing Techniques Involving Thin Films for Studying Biomolecular Interactions and Membrane Fouling Phenomena

5.1 Introduction

5.2 Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D)

5.3 Surface Plasmon Resonance (SPR)

5.4 Applications of SPR and QCM-D

5.5 Conclusions

Acknowledgements

References

Chapter 6: Smart Membrane Surfaces: Wettability Amplification and Self-Healing

6.1 Introduction

6.2 Basics of surface wettability

6.3 Amplified Wettability

6.4 Actuation Mechanisms

6.5 Self-Powered Liquid Motion

6.6 Self-Cleaning Mechanisms

6.7 Self-Healing Concepts And Strategies

6.8 Repairable Surface Properties

6.9 Conclusions and Perspectives

References

Chapter 7: Model Bio-Membranes Investigated by AFM and AFS: A Suitable Tool to Unravel Lipid Organization and their Interaction with Proteins

7.1 Introduction

7.2 Supported Lipid Bilayers

7.3 Atomic Force Microscopy (AFM) and Phase Behavior of LBs

7.4 Atomic Force Spectroscopy (AFS) of Supported Lipid Bilayers

7.5 Lipid/Protein Interactions

7.6 Conclusions

References

Part 3: Directed Molecular Separation

Chapter 8: Self-Assembled Nanoporous Membranes for Controlled Drug Release and Bioseparation

8.1 Introduction

8.2 General Aspects of Block Copolymer Self-Assembly

8.3 Block Copolymer-Based Membranes

8.4 Fabrication of Nanoporous Membranes Derived from Block Copolymers

8.5 Tunability of Surface Properties

8.6 Application of Block Copolymer-Derived Membranes to Bioseparation and Controlled Drug Release

8.7 Conclusion

References

Abbreviations

Chapter 9: Hybrid Mesoporous Silica for Drug Targeting

9.1 Introduction

9.2 Synthesis and Characterization of Bifunctional Hybrid Mesoporous Silica Nanoparticles Potentially Useful for Drug Targeting

9.3 Drug-Loaded Folic-Acid-Grafted MSNs Specifically Target FR Expressing Tumour Cells [16]

9.4 Conclusion

References

Chapter 10: Molecular Recognition-driven Membrane Processes

10.1 Molecular Imprinting Technique

10.2 Affinity Membranes

10.3 Cyclodextrins As Molecular Recognition Elements

10.4 Zeolite Membranes as Molecular Recognition Devices: Preparation and Characterization

10.5 Functionalized Particles-loaded Membranes For Selective Separation Based On Molecular Recognition

10.6 Biphasic Enzyme Membrane Systems with Enantioselective Recognition Properties ror Kinetic Resolution

10.7 Membrane Surface Modification

References

Part 4: Membrane Sensors and Challenged Applications

Chapter 11: Electrospun Membranes for Sensors Applications

11.1 Introduction

11.2 Basic Principles of Electrospinning

11.3 Control of the Electrospinning Process

11.4 Application of Electrospun Materials to Ultrasensitive Sensors

11.5 Conclusions

Abbreviations

References

Chapter 12: Smart Sensing Scaffolds

12.1 Introduction

12.2 Composite Sensing Biomaterial Preparation

12.3 Composite Sensing Biomaterial Characterisation

12.4 SWNTs-Based Composite Films Structural Properties

12.5 Tensile Properties of SWNTs-Based C omposite Films

12.6 Electrical Properties of SWNTs-Based Composites Films

12.7 Electromechanical Characterisation and Strain-Dependence Measurement

12.8 Cell Sensing Scaffolds

12.9 Processing of CNT Composite: Microfabrication of Sensing Scaffold

12.10 Conclusions

References

Chapter 13: Nanostructured Sensing Emulsion Droplets and Particles: Properties and Formulation by Membrane Emulsification

13.1 Introduction

13.2 Emulsions and Emulsification Methods

13.3 Senging Particles Produced by Membrane-Based Process

13.4 Conclusions

References

Chapter 14: Membranes for Ultra-Smart Textiles

14.1 Introduction

14.2 Membranes and Comfort

14.3 Adaptive Membranes for Smart Textiles

14.4 Barrier Functions of Membranes

14.5 Membrane Materials for Self-cleaning Function

14.6 Interactive Membranes for Wearable Electronics

14.7 Conclusions and Prospects

References

Index

Smart Membranes and Sensors

Scrivener Publishing 100 Cummings Center, Suite 541J Beverly, MA 01915-6106

Publishers at Scrivener Martin Scrivener([email protected]) Phillip Carmical ([email protected])

Copyright © 2014 by Scrivener Publishing LLC. All rights reserved.

Co-published by John Wiley & Sons, Inc. Hoboken, New Jersey, and Scrivener Publishing LLC, Salem, Massachusetts. Published simultaneously in Canada.

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Library of Congress Cataloging-in-Publication Data:

ISBN 978-1-118-42379-0

To my Lovely Family and Honey Billa

Preface

Unquestionably, the human being is the organism provided with the finest perception, because he is the most complex system of receptors of heat, cool, sounds, light and smells. In the human body, physical/chemical agents, in fact, pass through biological membranes reaching the receptors, while electrical signals are transmitted to the brain through nerve networks. The brain transduces marvelously each single response into a sensation.

With this awareness, many scientists have attempted to reproduce artificial sensing systems over the last years, trying to mimic natural structures and processes. Despite how arduous the accomplishment of such a task seemed, many efforts were made in this direction, moving from ‘sense’ to ‘sense-to-react’ systems. Today the major ambition is to go further. The desired target is the creation of ultra-smart systems, wherein the functions of sensing, acting and adapting are sequentially integrated. Within this frame work, the membranes can play a key role in the build up of complex arrays, where complementary smart functions can be allocated and integrated. Indeed, the molecular manipulation in membranes allows effectively to tailor desired properties on different length scales, supplying confined functional spaces and geometries for storage, release, separation, chemical reaction, energy/mass transfer, but also for shield/microclimate regulation, cleaning, fluid flows on molecular length scale, controlled cell growth, high-throughput screening for biological processes interrogation (and so on).

In this context, it is convenient to introduce briefly the concepts of membrane and sensor. The former is a semipermeable interface enabling the selective passage of molecular species, while blocking others. The latter signifies a device capable of detecting a physical, chemical or electrical response, which is converted by a transducer into a signal immediately perceptible by the human eye or measurable on an instrument. It so happens that, when a detection function is coupled with an adaptive transport, the membrane works as an ultra-smart system. In this way, the membrane adapts itself to surrounding environment, adjusting its own structure and chemistry in order to regulate mass/energy flow and/or transfer signals/information in response to external physical and/or chemical inputs.

In this perspective, adaptive membranes are expected to accelerate the passage from smart to ultra-smart systems, bringing large benefits to many technologically sophisticated areas such as telemedicine, microfluidics, drug delivery targeting, (bio)separation, textiles, clean power production, environment monitoring, agro-food safety, cosmetics, architecture, and automotive and so on. The use of membrane sensors becomes much more attractive if the modular scalability of the membrane technology is considered. A wider potential of smart membranes-based systems may be explored in the design of integrated industrial plants as well as in the creation of miniaturized devices, where molecular objects can sense and respond on one chip.

Numerous publications emerged in the literature dealing with sensing materials or membrane separations distinctly. Few of these contributions, however, are dedicated to dealing with sensor-like membranes. The intent of this book is to join these two concepts catalyzing the process of integration between complementary disciplines in order to share knowledge and expertise on this matter and construct a mutual language which can draw many and many researchers, investigators, graduated students and final users in the world of the smart science and technology.

This book contains insightful contributions from scientists working in the field of sensor materials and membranes. It covers various points of view, including the choice of materials and techniques for assembling responsive membranes and interfaces with ability to transport mass and energy on demand, along with the description of appropriate techniques for monitoring molecular scale events, which regulate the smartness of multifunctional objects needed to the accomplishment of developed applications.

Part I comprises three chapters, which deal with some sensors materials for membranes such as carbon nanotubes, ionic liquids, and light-responsive hydrogels, along with self-assembling lipids, polymers, and small molecules for the fabrication of perm-selective membranes and vesicular structures with ability to work as submicro-reactors, catalysts and drug delivery vehicles.

Part II is entirely dedicated to the description of molecular interactions, which cause the interfaces to self-adjust and restore morphology, chemistry and charge for preserving original properties against hostile external conditions, self-powering molecular diffusion and directing biomolecule recognition. Weak interactions that dominate the world of self-assembled materials and supra-molecular structures are discussed from a theoretical and experimental point of view.

In Part III, three chapters describe molecular recognition mechanisms directed to control drug release and bioseparation. Following an overview on self-assembled nanoporous membranes used as platforms for biosensors, an extensive discussion is dedicated to the fabrication of membranes bearing recognition sites and their use in bioseparation processes; the responsive activity of mesoporous silica nanoparticles, zeolites, molecularly imprinted membranes, biomemitic affinity membranes, and membranes containing cyclodextrins is examined.

In Part IV, four advanced applications of like-sensors membranes are presented: electrospun membranes for the construction of ultrasensitive sensors, which facilitate analyte adsorption, mass and electric charge transport; 3-D conductive scaffolds enabling one to monitor cell behavior, study chronic disease models, and repeat dose experiments; sensing particles prepared by membrane emulsification and with ability to transport active substances and/or convert chemical and biochemical signals into optical, electrical, thermal and mechanical signals; adaptive membranes for ultra-smart textiles, which can provide self-maintenance, adaptability, auto-adjustment and long-distance communication through heat storage and thermo-regulation, modular breathability, protection, self-cleaning, odor capture and drug delivery as well as electrical signal transmission.

I am very pleased to have edited this book and I am very grateful to each of the contributors for their dedication and cooperation. This book would not have been possible without their enthusiasm to share knowledge, passion and time. My hope is that everyone enjoys reading and using this cross-disciplinary discussion for bringing innovation to there own research.

Annarosa Gugliuzza July 2014

Part 1

SENSING MATERIALS FOR SMART MEMBRANES

Chapter 1

Interfaces Based on Carbon Nanotubes, Ionic Liquids and Polymer Matrices for Sensing and Membrane Separation Applications

María Belén Serrano-Santos*, Ana Corres Ortega and Thomas Schäfer

POLYMAT, University of the Basque Country, Donostia-San Sebastián, Spain

*Corresponding author: [email protected]

Abstract

The combination of carbon nanotubes with widely tunable materials such as ionic liquids and polymers theoretically provides a tremendous degree of freedom for designing thin films (membranes) for specific sensing and separation applications. Not surprisingly, a plethora of applications has been reported in literature primarily for sensing devices. This chapter discusses some selected case studies which illustrate, on one hand, the exciting new opportunities which a combination of these materials offer; on the other, it stresses the strong need for evaluating their potential in the context of existing devices such as to appreciate their true benefit.

Keywords: Ionic liquids, polymer membranes, carbon nanotube hybrids, thin film sensors

1.1 Introduction

Sensing and membrane separation applications seem, at first sight, two very distinct areas of applications of interfaces. However, both have in common that their very first step and at times overall performance is governed by a selective interface establishing a selective interaction with desired compounds (Figure 1.1). Subsequently, this interaction has in most cases be transduced into a signal in sensors, or result in a transport of compounds across the interface in membranes, two phenomena which may require adaptation and possibly even compromising to some extent the pristine properties of the interface for the benefit of an overall improved performance. Therefore, a high intrinsic selectivity of interfaces and possibly a high degree of adaptation is indispensable. Sensor and membrane interfaces have, hence, in common that both require a maximum selectivity for target compounds. Membranes allow furthermore an optimization of the preferential transport of the target compounds across the interface. The complementarity of both sensors and membranes can therefore give rise to hybrid systems of enhanced overall performance [1].

Figure 1.1(a) In sensor applications, a selective interface warrants the interaction with a desired sample or target (1), resulting in an uptake, adsorption or recognition event, (2), which then is transduced into an output signal such as an electric current or an optical signal; (b) in membrane applications, the same interface can be used to preferentially concentrate or recognize desired compounds present upstream like in sensors (1), but these compounds then diffuse, convectively flow or are transported across the interface (2) and leading to an increase in the concentration downstream (3). Both concepts can also be combined, for example, to generate what may be considered “smart membranes”.

Polymers are excellent matrices for such interfaces owing to their versatility, tremendous range of possible physico-chemical properties and their tunability. However, modifying the physico-chemical properties of polymers may go along with an undesired change in their mechanical properties. For example, polydimethylsiloxane (PDMS), widely known as silicone is a mechanically flexible polymer suitable for creating thin films as selective interfaces as much as self-standing thick films. Although the material is hydrophobic, its hydrophobicity and hence affinity for certain organic compounds can be further increased by gradually substituting short-chain methyl groups by longer-chain octyl groups. While the resulting polyoctylmethylsiloxane (POMS) yields thin films of significantly improved selectivity, its mechanical stability suffers slightly such as to not permit stable self-standing thick-films [2]. This drawback is of little relevance in practice where the focus is on supported thin films, such as is the case in sensor applications [3], but it illustrates that physico-chemical and mechanical properties are often interdependent.

As a consequence, hybrid materials or mixed-matrix materials are often conceived of that try to combine the best of several worlds into a single matrix. In this case, a support material providing the mechanical stability such as a polymer is doped with additives or carriers that further increase the selectivity of the interface. In such a modular system, one seeks to use as dopant another versatile material whose selectivity can be optimized without considering mechanical requirements, as these are taken care of by the support materials. In the following, examples of using ionic liquids and carbon nanotubes as materials for interfaces, individually or combined – also with other materials such as polymers - will be discussed. Rather than giving an exhaustive overview of the field which covers a tremendous amount of research articles published over the last 10–15 years, it will focus on individual case-studies in order to discuss in more detail key aspects of the respective applications.

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