Electrospinning for High Performance Sensors (eBook)

Antonella Macagnano, is a research scientist at the National Research Council (2001-, CNR). She started her activity at the Institute for Microelectronics and Microsystems (IMM-Rome, Italy) until 2013 when she moved to the Institute of Atmospheric Pollutant Research (IIA) where she has been leading an action called “High-Performance Sensors and Sensing Systems for Monitoring Air Quality and Environment”. She devoted most of her research activity to design and develop sensors and sensor arrays, with different principles of transduction, based on biomimetics and bioinspired artificial sensing membranes. She received the Biological Science’s Degree in 1993 at Lecce University and the Professional’s Degree in 1994. Since 1996 she has been cooperating with many National and International Institutions for designing and studying novel sensors (gravimetric, conductive, capacitive) and sensing strategies for environmental and biomedical applications, within several projects (among them, seven as a leader). She has also been involved in studying and developing novel and integrated systems to detect organic substances and dusts in space explorations. More recently, she has been focusing on the sensing performances of organics, inorganics and composite nanofibers obtained through the implementation of the electrospinning technology. She is member of the European COST Action (MP1206), which is aiming to create a European multidisciplinary knowledge platform on electrospinning of nanofibres to facilitate their rapid development and applications. She is author of several international papers on the topic, book contributions as well as talks and invited talks in international meetings. She was the Chair of the International Workshop in Rome (2014) titled “Electrospinning for High Performance Sensing”.Erich Kny, founder and director of KEMYK Consulting (2012-, Vienna, Austria), studied Chemistry and Physics at Vienna University. After some years teaching at the Department of Physical Chemistry of the University of Vienna he spent two years as a Postdoc at the Materials Research Centre at the University of Missouri, Rolla, USA doing research in Plasma-polymerization and surface analysis. After returning to Austria he was employed at the Metallwerk Plansee in Austria for the next ten years where he did research and development work in powder metallurgy, refractory metals, hard metals, refractory metals components for fusion research and superconductor development. After this industrial experience he became head of the Engineering Department (comprising the four institutes dealing with Materials research, Automation, Process technology and Mechanical Engineering) at the Austrian Research Centre. He held this position for 17 years. After retirement from the Austrian Research Centre he founded his own consulting company KEMYK in 2011. He was chair of the COST Action MP701 on Polymer Nanocomposites and is presently chair of the COST Action MP1206 on Electrospinning. He published well over 100 publications, 3 book contributions, several patents and was lately the editor of the conference symposium proceedings at the EMRS 2009 on Polymer Nanocomposites.Emiliano Zampetti, is research scientist (non-permanent position) at the Institute of Atmospheric Pollutant Research (IIA-CNR) (Rome, Italy, 2014-) of the National Research Council. He received the master degree in Electronics Engineering in 2002 and the PhD on Engineering of Sensorial and Learning Systems in 2007 from University of Tor Vergata, in Rome. He cooperated with several Institutions within International and National Projects and worked as a researcher at the Institute of Microelectronics and Microsystems (IMM-CNR) (2008-2013). His research interests are concerned with the design and development of the electronic circuits for electronic nose systems, electronic readout circuits for gas sensor, customized designs of transducers and integrated equipment for sensing gas and volatile organic compounds, electrospinning apparatus for nanotechnology applications and bio-electronic noise in cells and neurons. He is author of dozens international and national papers as well as international talks.

Preface 8
Contents 10
Introduction to Electrospinning for High Performance Sensors 12
Electrospinning and the COST Action MP1206 16
Chapter 1: Facile and Ultrasensitive Sensors Based on Electrospinning-Netting Nanofibers/Nets 19
1.1 Introduction 19
1.2 Electrospinning and Electro-Spinning/Netting (ESN) 21
1.2.1 Electrospinning 21
1.2.1.1 The Process of Electrospinning 21
1.2.1.2 Rich and Varied Electrospun Nanofibers 21
1.2.2 ESN Technique 25
1.2.2.1 History of ESN 25
1.2.2.2 Formation Mechanism of NFN Membrane 26
1.2.2.3 NFN Membrane Based on Different Polymer Systems 28
1.3 Sensors Based on Electrospun Nanofibers and ESN NFN Membranes 30
1.3.1 QCM Sensors 31
1.3.1.1 PEI Functionalized Polystyrene (PEI@PS) Nanofibrous Membranes Based Formaldehyde Sensors 32
1.3.1.2 PEI Functionalized Titanium Dioxide (PEI@TiO2) Nanofibrous Membranes Based Formaldehyde Sensors 32
1.3.1.3 PEI Functionalized PA-6 NFN Membranes Based Formaldehyde Sensors 35
1.3.2 Colorimetric Sensors 37
1.3.2.1 Colorimetric Strips for Formaldehyde Assaying 38
1.3.2.2 Colorimetric Strips for Mercury (II) Ions 39
1.3.2.3 Colorimetric Strips for Lead (II) Ions 41
1.4 Summary and Perspectives 43
References 45
Chapter 2: Controlling the Nanostructure of Electrospun Polymeric Fibers 53
2.1 Introduction 54
2.2 Polymer Dynamics During Electrospinning 56
2.3 X-ray Imaging of Electrospinning Jets 62
2.4 Entanglement Loss and Short Nanofibers 66
2.5 Fiber Nanostructure and Mechanical Properties 71
2.6 Chain Orientation in Fibers 74
2.7 Controlling the Nanostructure 79
References 80
Chapter 3: Graphene-Based Composite Materials for Chemical Sensor Application 83
3.1 Chemical Sensors 83
3.2 Graphene-Based Sensing Layers 84
3.3 Nanoparticle-Graphene Composite Sensing Layers 89
3.3.1 Metal NP-Graphene Gas Composite Sensing Layers 90
3.3.2 Metal Oxide NP-Graphene Composite Sensing Layers 95
3.3.3 Metal-Metal Oxide NP Hybrid-Graphene Composite Sensing Layers 99
3.4 1D Structure-Graphene Composite Sensing Layers 102
3.4.1 Metal Oxide-Graphene Composite Sensing Layers 104
3.4.2 Polymer-Graphene Composite Sensing Layers 110
3.4.3 Carbon Nanotubes (CNTs)-Graphene Composite Sensing Layers 113
3.5 Summary and Future Prospects 113
References 114
Chapter 4: Electrospinning of Electro-Active Materials: Devices Based on Individual and Crossed Nanofibers 120
4.1 Introduction 120
4.2 Experimental 122
4.2.1 Electrospinning 122
4.2.2 Gas Sensor 123
4.2.3 Diode 123
4.2.4 Electrical Characterization 125
4.3 Discussion 125
4.3.1 Gas Sensor 125
4.3.2 Diode 126
4.4 Conclusions 129
References 130
Chapter 5: Photoconductive Electrospun Titania Nanofibres to Develop Gas Sensors Operating at Room Temperature 131
5.1 Introduction 131
5.2 Electrospun Titania Based Gas Sensors 132
5.3 Photoconductive Electrospun TiO2 Nanofibres Based Gas Sensors 134
5.3.1 Photoconductive Chemoresistor Based on TiO2 Nanofibres 134
5.3.1.1 Sensor Responses Towards Humidity, Ammonia and Nitrogen Dioxide 136
5.3.2 Photoconductive Chemiresistor Based on TiO2 Nanofibres Decorated with Pt Nanoparticles 137
5.3.2.1 Sensor Responses Towards Hydrogen at Room Temperature 140
References 141
Chapter 6: Electrospun Fluorescent Nanofibers and Their Application in Optical Sensing 145
6.1 Introduction 145
6.2 Nanofiber-Based Light-Emitting Systems 146
6.2.1 Quantum Dot- and Dye-Doped Electrospun Nanofibers 147
6.2.2 Nanofibers Embedding Bio-chromophores 149
6.2.3 Nanofibers Made by Conjugated Polymers 149
6.2.4 Luminescent Nanofiber Arrays 151
6.3 Emission Properties of Electrospun Nanofibers 153
6.3.1 Spectral Properties of Photoluminescence of Electrospun Fibers 154
6.3.2 Emission Quantum Yield and Lifetime 155
6.3.3 Polarization of the Emission 156
6.4 Optical Sensing by Modulating Emission Intensity 157
6.4.1 Metal Ions 159
6.4.2 Explosive Compounds 159
6.4.3 Optical Biosensing 161
6.5 Other Optical Sensing Mechanisms: Waveguiding 165
6.6 Conclusions and Perspectives 167
References 167
Chapter 7: Nanofibre-Based Sensors for Visual and Optical Monitoring 172
7.1 Introduction 173
7.2 Principles of Colorimetric and Fluorescence Sensing Mechanisms 174
7.2.1 Absorbance-Based Sensing 174
7.2.2 Fluorescence-Based Sensing 175
7.2.3 Materials for Colorimetric and Fluorescence Sensing 177
7.3 Nanofibrous Sensors Based on Dye-Doping 178
7.3.1 Dye-Doping: A Fast and Easy Procedure for the Production of Colorimetric and Fluorescent Nanofibres 178
7.3.2 The Power of Molecular Modelling of a Dye and a Dye-Doped System 180
7.3.3 The Main Problem of the Dye-Doping Technique: Dye-Migration 181
7.4 Nanofibrous Sensors Based on Functional Polymers 182
7.4.1 Functionalized Polymers 182
7.4.2 Conjugated Polymers 183
7.5 The Potential of Colorimetric and Fluorescent Sensors for Visual and Optical Monitoring: Applications 184
7.5.1 Environmental Monitoring and Safety 184
7.5.2 Biomedical Sciences 188
7.5.3 Others 189
References 189
Chapter 8: Electrospun Fluorescent Nanofibers for Explosive Detection 193
8.1 Introduction 193
8.2 Colorimetric Detection 194
8.3 Smart Hybrid Sensor 198
8.3.1 Fluorescent Electrospun Nanofibers for Explosive Detection 203
8.4 Conclusions 213
References 215
Chapter 9: Nanoparticle/Nanochannels-Based Electrochemical Biosensors 219
9.1 Electrochemical Biosensors and Nanomaterials 219
9.1.1 Use of Nanoparticles in Electrochemical Biosensors: Gold Nanoparticles 221
9.1.2 Nanochannels 222
9.1.2.1 Sensing Using Nanochannels: From the Coulter Counter to the Stochastic Sensing 222
9.1.2.2 Solid-State Nanochannel Arrays Preparation 224
9.2 Highly Ordered Mesoporous Thin Film Formation by Nanoparticle Assembling 224
9.3 Micro-/Nanomolding Techniques: Nanoimprint Lithography 225
9.4 Metallic Substrates Anodization: Anodic Aluminum Oxide Nanoporous Membranes Preparation 226
9.5 Solid-State Nanochannel Arrays Functionalization 227
9.6 Electrochemical Biosensing Systems Based on Solid-State Nanochannel Arrays 228
9.6.1 Detection Principle 228
9.6.2 Application for Protein Biomarkers Detection 230
9.6.3 Application for DNA Detection 233
9.7 Conclusions 233
References 234
Chapter 10: Electrospinning-Based Nanobiosensors 238
10.1 Introduction 239
10.2 Enzyme-Based Nanobiosensors 243
10.2.1 Enzyme Immobilisation 243
10.2.2 Enzyme Nanobiosensors 249
10.2.2.1 Glucose Nanobiosensors 250
10.3 (Bio)Affinity Nanobiosensors 254
10.3.1 DNA-Based Nanobiosensors 254
10.3.1.1 Recognition Systems 256
DNA Hybridisation 256
Aptamers 256
Nucleic Acid Enzymes (NAEs) (Ribozymes+DNAzymes) 257
Aptazymes 258
Peptide Nucleic Acids (PNAs) 259
10.3.1.2 DNA Nanobiosensors 260
DNA Hybridisation Nanobiosensors 260
Our Development of a Nanofibrous DNA-Based Biosensor 262
FNAs Nanobiosensors 269
Aptamers Biosensors 270
Aptazyme, DNAzyme and Ribozyme Biosensors 272
Peptide Nucleic Acids (PNAs) Biosensors 272
10.3.2 Immunosensors 274
10.3.2.1 Immunosensors Through Electrospinning 275
10.3.2.2 Our Development of an Electrospun Nanofibrous Immunosensor 278
10.4 Outlooks 281
References 282
Chapter 11: Development by Electrohydrodynamic Processing of Heat Storage Materials for Multisectorial Applications 293
11.1 Introduction 294
11.1.1 Electrospinning for Energy Applications 294
11.1.2 Use of Electrospinning for PCM´S Encapsulation 294
11.1.2.1 PCMs for the Protection of Thermo-sensitive Products 295
11.1.2.2 PCMs for Textile Applications 297
11.1.2.3 PCMs for Building Materials 298
11.2 Conclusions 299
References 299
Chapter 12: Co-electrospun Brain Mimetic Hollow Microfibres Fibres for Diffusion Magnetic Resonance Imaging 300
12.1 Introduction 301
12.1.1 Diffusion MRI 301
12.1.2 MRI Phantoms 302
12.1.2.1 Imaging Phantoms 302
12.1.2.2 Brain Mimicking Phantoms 302
12.1.2.3 Natural and Synthetic Phantoms 303
12.2 Hollow Microfibres by Co-electrospinning 304
12.2.1 Co-electrospinning 304
12.2.2 Co-ES Hollow Microfibres 304
12.2.2.1 Random Hollow Microfibres 304
12.2.2.2 Aligned Hollow Microfibre Bundles and Strips 306
12.3 Co-ES Microfibre Phantoms and MR Evaluation 311
12.3.1 Fibre Bundle Based MR Phantoms 311
12.3.2 Fibre Strip-Based MR Phantoms 313
12.4 Conclusions 314
References 314
Chapter 13: Turning Nanofibres into Products: Electrospinning from a Manufacturer´s Perspective 316
13.1 Introduction 316
13.2 The Electrospinning Industry 318
13.2.1 Commercial-Scale Electrospinning 320
13.2.1.1 Needle-Based Electrospinning 320
13.2.1.2 Needleless Electrospinning 322
13.3 Companies Involved in the Electrospinning Industry 323
13.4 Alternative Industrial Nanofibre Manufacturing Technologies 323
13.4.1 Islands-in-the-Sea or Segmented Pie Extrusion 324
13.4.2 Melt Blowing 324
13.4.2.1 Forcespinning and Rotary Jet Spinning 325
13.5 Challenges Faced by Commercial Electrospinning Companies 325
13.5.1 Building a New Market for Nanofibre 326
13.5.2 Production Rates and Solvents 327
13.5.3 Managing a Platform Technology 328
13.5.4 Engaging with Manufacturers Too Late in Development 328
13.5.5 Papers, Patents and PhD´s 329
13.5.6 Lack of Control Over Raw Materials Supply and Consistency 330
13.5.7 Nano-fear and the Absence of Regulation 331
13.6 Commercially Available Electrospun Products 332
13.6.1 Nanofibres in Filtration Applications 333
13.6.2 Nanofibres in Composite Applications 334
13.6.3 Nanofibres in Acoustic Applications 335
13.6.4 Nanofibre for Medical and Skincare Applications 335
13.6.5 Nanofibres for Sensing Applications 337
13.7 Summary and Future Outlook 339