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This thesis aims at providing a better understanding of the micro- and nanofabrication of conducting polymers for biomedical devices and presents novel processes that widen the application range of conducting polymers in this field. The thesis is divided in four chapters, namely "Materials and Methods", "Biocatalytically-produced polypyrrole thin films and microelectrodes on insulating surfaces", "Azide-PEDOT electrodes. Application to DNA sensors" and "Fabrication of polypyrrole single nanowire devices". Chapter 1, entitled "Materials and Methods", describes the materials used in this work and the fabrication and characterization methods required for the development of the thesis. Here, theoretical and experimental details about the techniques employed, are provided. Chapter 2, entitled "Biocatalytically-produced polypyrrole thin films and microelectrodes on insulating surfaces", presents a new on-surface biocatalytical procedure for the fabrication of polypyrrole microelectrodes on insulating surfaces, with resolutions comparable to the ones of conventional photolitography. This is an environmentally respectful microfabrication method that allows the entrapment of biomolecules during the polymer synthesis in a single step. As a proof of concept, biotin was trapped in the polypyrrole matrix and then released in a controlled way through electrical stimulation. It was proven that the polymer keeps its electroactivity after the fabrication and functionalization processes. This biocatalytical-based technique represents a straightforward method for the microfabrication of biological-active conducting polymers, which could be implemented in implantable devices for remotely controlled tissue interactions. Chapter 3, entitled "Azide-PEDOT electrodes. Application to DNA sensors", describes the fabrication and testing of an electrochemical label-free DNA hybridization sensor, based on novel azidomethyl-modified poly(3,4-ethylenedioxythiophene) electrodes (azide-PEDOT electrodes). These azide-PEDOT electrodes were used as platforms for the immobilization of acetylene-DNA probes, complementary to the "Hepatitis C" virus. The acetylene-DNA probes were covalently grafted to the polymer backbone via the robust "Click" reaction, which a part from being a very selective functionalization method, preserves DNA from denaturation during the synthesis of the polymer. DNA hybridization was detected by Differential Pulse Voltammetry (DPV), where the electrochemical change of the polymer behaviour, produced by the recognition event, was directly evaluated. This fabrication procedure is a powerful tool for the preparation of label-free DNA sensors able to selectively recognize a specific DNA sequence, down to the nanomolar range. Finally, Chapter 4, entitled "Fabrication of polypyrrole single nanowire devices", discusses the fabrication of polypyrrole at the nanoscale. Two fabrication techniques were investigated here, namely dip pen nanolithography and electrochemical polymerization on template-assisted surfaces. On one hand, the dip pen nanolithography proved to be a simple deposition technique with good control over size and location of the polypyrrole nanowires. On the other hand, the electrochemical polymerization on template-assisted surfaces provided as well nanoscaled polypyrrole, but added the possibility to chemically manipulate the polymer. This chemical manipulation was translated into polymer devices with different electrical properties. By the use of these techniques, the capability of fabricating single nanowire devices (ready to use in different applications) and arrays of ordered nanowires based on conducting polymers is demonstrated. Additionally, two appendixes can be found at the end of the thesis: Appendix A: "Fabrication of azide-PEDOT microwire-based devices" and Appendix B: "Fabrication of nanopatterns by electron-sensitive silanes". They provide short experimental results obtained during the course of this work, which are first steps for future investigations. A general conclusions section can be found at the end of the thesis, where a summary of the main achievements and contributions of this thesis are listed.
Conducting Polymers with Micro or Nanometer Structure describes a topic discovered by three winners of the Nobel Prize in Chemistry in 2000: Alan J. Heeger, University of California at Santa Barbara, Alan G. MacDiarmid at the University of Pennsylvania, and Hideki Shirakawa at the University of Tsukuba. Since then, the unique properties of conducting polymers have led to promising applications in functional materials and technologies. The book first briefly summarizes the main concepts of conducting polymers before introducing micro/nanostructured conducting polymers dealing with their synthesis, structural characterizations, formation mechanisms, physical and chemical properties, and potential applications in nanomaterials and nanotechnology. The book is intended for researchers in the related fields of chemistry, physics, materials, nanomaterials and nanodevices. Meixiang Wan is a professor at the Institute of Chemistry, Chinese Academy of Sciences, Beijing.
Until about 30 years ago all carbon-based polymers were regarded strictly as insulators, and hence were extensively utilized by the electronics industry for this very property. They have been used as inactive packaging and insulating material. This very narrow perspective has rapidly changed with the emergence of intrinsically conducting polymers. The combination of conventional polymers with conductive polymers or fillers is an important alternative to obtaining new polymeric materials with designed properties. Through the combination of conventional polymers with conductive polymers such as polyaniline, polypyrrole, and so on, the mechanical properties of conducting polymers can be improved. The insulating polymer removes the brittleness and lack of processibility that are the main drawbacks hindering conducting polymers. Blend applications require that conductivity is achieved at a small weight fraction of conducting polymer. There is also an increased requirement for polymeric materials whose electrical conductivity can be tailored. The aim this chapter is to describe conducting polymer blend systems to identify characteristic trends that might be useful for the investigation of their potential application in various electronic and optoelectronic devices.
Since the establishment of the conductive properties of intrinsic conductive polymers, a huge variety of basic and applied research has been carried out, involving different polymers, copolymers, blends, mixtures and composites. Thus, fundamental understanding of physical and chemical properties of these materials has been sought, while the applied aspects have advanced very rapidly, crossing the boundaries between disciplines. Today, the applications of conducting polymers in various fields such as neuroscience, nanotechnology and green chemistry, are easily found. This development is dynamic and it needs to be updated and hence the motivation for the set of results presented in this book; which provides information about the development of fundamentals, and about some applications of conductive polymers.
The pioneering work by Nobel Prize Laureates Heeger, MacDiarmid, and Shirakawa marked the birth of conductive polymers, a new family of revolutionary organic materials at the boundaries between classic plastics, metals, and semiconductors. Since then, a host of chemically diverse conducting polymeric structures has been devised with fascinating optical, electrical, magnetic, and redox properties that can be tuned using easy chemical/electrochemical doping. In recent decades, the combination and blend of conductive polymers with other materials families (e.g., carbon nanomaterials, metal nanoparticles or oxide nanostructures, common polymers, and resins) fostered the advent of a new generation of hybrid multifunctional composites with enhanced properties and high potential for present and near-future everyday life applications, ranging from photovoltaics, OLEDs, smart windows and garments, plastic batteries for sensors, and intelligent actuators. In this book, we compile some of the latest advances in the field, covering both old issues and new examples emphasizing emerging applications in biomedical science, healthcare, separation science, and water pollution abatement.
Providing a vital link between nanotechnology and conductive polymers, this book covers advances in topics of this interdisciplinary area. In each chapter, there is a discussion of current research issues while reviewing the background of the topic. The selection of topics and contributors from around the globe make this text an outstanding resource for researchers involved in the field of nanomaterials or polymer materials design. The book is divided into three sections: From Conductive Polymers to Nanotechnology, Synthesis and Characterization, and Applications.
This second edition of a well-received volume has been thoroughly updated and expanded to cover the most recent developments. Coverage now includes additional polymers such as polyindole and polyazines, composites of polymers with carbon nanotubes, metals, and metal oxides, as well as bending-beam techniques for characterization. Again, the author provides a systematic survey of the knowledge accumulated in this field in the last thirty years. This includes thermodynamic aspects, the theory of the mechanism of charge transport processes, the chemical and physical properties of these compounds, the techniques of characterization, the chemical and electrochemical methods of synthesis as well as the application of these systems. The book contains a compilation of the polymers prepared so far and covers the relevant literature with almost 2000 references. From reviews of the previous edition ‘a comprehensive reference guide for those interested in this field’ (Journal of Solid State Electrochemistry)
This book presents a comprehensive survey about conducting polymers and their hybrids with different materials. It highlights the topics pertinent to research and development in academia and in the industry. The book thus discusses the preparation and characterization of these materials, as well as materials properties and their processing. The current challenges in the field are addressed, and an outline on new and even futuristic approaches is given. “Conducting Polymer Hybrids” is concerned with a fascinating class of materials with the promise for wide-ranging applications, including energy generation and storage, supercapacitors, electronics, display technologies, sensing, environmental and biomedical applications. The book covers a large variety of systems: one-, two-, and three-dimenstional composites and hybrids, mixed at micro- and nanolevel.
Plastics are materials composed of many long chains of molecules with repeating subunits; strong interactions between neighboring molecules lead to the material used throughout the world. Plastics are commonly thought to be insulating, in stark contrast to the conductivity of metals. However, certain polymer structures were discovered to exhibit semiconducting properties, the subject of the Nobel Prize in Chemistry in 2000. Conducting polymers have a unique molecular structure with an electronically conjugated backbone, allowing electrons to freely travel both across the chain and in between chains. This work focuses on controlling the kinetics of the reaction between the vapors of an aromatic heterocycle pyrrole and aqueous iron(III) containing oxidants. With the methods introduced in this dissertation, the conducting polymer polypyrrole is formed with great control of molecular structure, allowing for the fine-tuning of properties like conductivity. Unique interactions during synthesis lead to the controlled deposition of polypyrrole nano- and microstructures, including fibers, tubes, webs, and thin films. These unique structures of polypyrrole are then analyzed for their performance as usable electronic materials, including transparent and flexible conductors as well as electrode materials for electrochemical energy storage devices.
This book outlines methods to improve functioning of these polymer based devices – in particular, the multi-faceted cognition of these materials. In situ electrochemical techniques are studied to elucidate redox switching between non-conducting and conducting states. The book examines the advantages of combinations of in situ electrochemical techniques in a hyphenated mode for analyzing conducting polymers.