The emergence of organic electronics - a technology that relies on carbon-based semiconductors to deliver devices with unique properties - represents one of the most dramatic developments of the past two decades. A rapidly emerging new direction in the field involves the interface with biology. The "soft" nature of organics offers better mechanical compatibility with tissue than traditional electronic materials, while their natural compatibility with mechanically flexible substrates suits the non-planar form factors often required for implants. More importantly, their ability to conduct ions in addition to electrons and holes opens up a new communication channel with biology. The coupling of electronics with living tissue holds the key to a variety of important life-enhancing technologies. One example is bioelectronic implants that record neural signals and/or electrically stimulate neurons. These devices offer unique opportunities to understand and treat conditions such as hearing and vision loss, epilepsy, brain degenerative diseases, and spinal cord injury.The engineering aspect of the work includes the development of a photolithographic process to integrate the conducting polymer poly(3,4-ethylenedioxythiophene: poly(styrene sulfonate) (PEDOT:PSS) with parylene C supports to make an active device. The technology is used to fabricate electrocorticography (ECoG) probes, high-speed transistors and wearable biosensors. The experimental work explores the fundamentals of communication at the interface between conducting polymers and the brain. It is shown that conducting polymers outperform conventional metallic electrodes for brain signals recording.Organic electrochemical transistors (OECTs) represent a step beyond conducting polymer electrodes. They consist of a conducting polymer channel in contact with an electrolyte. When a gate electrode excites an ionic current in the electrolyte, ions enter the polymer film and change its conductivity. Since a small amount of ions can effectively "block" the transistor channel, these devices offer significant amplification in ion-to-electron transduction. Using the developed technology a high-speed and high-density OECTs array is presented. The dense architecture of the array improves the resolution of the recording from neural networks and the transistors temporal response are 100 μs, significantly faster than the action potential. The experimental transistor responses are fit and modeled in order to optimize the gain of the transistor. Using the model, an OECT with two orders of magnitude higher normalized transconductance per channel width is fabricated as compared to Silicon-based field effect transistors. Furthermore, the OECTs are integrated to a highly conformable ECoG probe. This is the first time that a transistor is used to record brain activities in vivo. It shows a far superior signal-to-noise-ratio (SNR) compare to electrodes. The high SNR of the OECT recordings enables the observation of activities from the surface of the brain that only a perpetrating probe can record. Finally, the application of OECTs for biosensing is explored. The bulk of the currently available biosensors often require complex liquid handling, and thus suffer from problems associated with leakage and contamination. The use of an organic electrochemical transistor for detection of lactate by integration of a room temperature ionic liquid in a gel-format, as a solid-state electrolyte is demonstrated.

Igor Stravinskys collaborations with contemporaries including Picasso, Nijinsky, and Cocteau are well documented. Less familiar, however, are the anachronistic collaborations suggested in one short movement Stravinsky wrote in 1918, and involving the Germans Luther and Bach, the Swiss Ramuz, the Russian Stravinsky, and the American Kurt Vonnegut Jr.<p> Grand Choral, the penultimate movement of Stravinskys lHistoire du Soldatwritten in 1918provides a key to unlocking the mysteries of construction, ideology, and by extension, performance of the work. Grand Choral parodies J.S. Bachs Cantata 80 (1715) which, in its turn, is based on Martin Luthers 1529 hymn, Ein feste Burg ist unser Gott. C.F. Ramuz, Stravinskys original collaborator on lHistoire du Soldat, based his libretto on a Russian folk tale, but in 1993, Vonnegut wrote a new text to accompany Stravinskys music, a text inspired by the true story of Private Eddie Slovik, the last American soldier executed for desertion. In essence, Vonnegut collaborates with Stravinsky in a posthumous sense, as Stravinsky does with Bach and Bach with Luther. Vonnegut and Stravinsky each write themselves into an existing work, giving it contemporary meaning and a new poignancy.<p> The principal aim of my paper is to document the process by which I studied and conducted lHistoire du Soldat with one libretto by Ramuz and another by Vonnegut. In the paper, I will first examine the historical context in which each of the collaborators contributed to lHistoire du Soldat. I will also present an analysis of Grand Choral with regard to the source material by Luther and Bach. Finally, I will document the process and findings of my study, rehearsal, and performance of each of the two versions of lHistoire du Soldat which I conducted on March 31, 2009 in Quance Theatre, on the campus of the University of Saskatchewan with a full cast of musicians, dancers and actors.

Materials based on novel Off-Stoichiometry Thiol-Ene polymers, abbreviated OSTE, show promising properties as materials forlow cost and scalable manufacturing of micro- and nanosystems such as lab-on-chip devices. The OSTE materials have tunablemechanical properties, offer possibility for low temperature bonding to many surfaces via tunable surface chemistry, and can beused in soft lithography. Unlike the commonly used elastomer poly(dimethylsiloxane), PDMS, the OSTE materials have lowpermeability for gasses, are resistant to common solvents and can be more permanently surface modified.In this master’s thesis project, the OSTE materials have been evaluated with focus on compatibility with cells, possibility fornanostructuring using soft lithography and the use of OSTE as a flexible support for conducting polymers.Results from cell seeding studies with HEP G2 cells suggest that cells can proliferate on a low thiol off-stoichiometry OSTEmaterial for at least five days. The biocompatibility for this type of OSTE material may be similar to poly(styrene). However, highlevels of free thiol monomers in the material decrease cell viability considerably.By using soft lithography techniques it is possible to fabricate OSTE nanochannels with at least the dimensions of 400 nm x 15nm. Combined with the advantages of using the OSTE materials, such as low temperature bonding and possibility for stablesurface modifications, a candidate construction material for future development of systems for DNA analysis is at hand.OSTE can serve as a flexible support for an adsorbed film of a conducting polymer with the possibility for future applicationssuch as electronic interfaces in microsystems. In this project, a film of PEDOT:PSS with the electrical resistance of ~5 kΩ wascreated by adsorption to an flexible OSTE material. Furthermore, results suggest that it is possible to further optimize theconductivity and water resistance of PEDOT:PSS films on OSTE.

Electrochemical polymerization of pyrrole functionalized polystyrene (PStPy) with pyrrole was carried out in water-sodium dodecyl sulfate solvent-electrolyte couple. Characterization of the resulting copolymer was performed via Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and four probe conductivity measurements. Glucose oxidase and polyphenol oxidase enzymes were immobilized in polypyrrole (PPy) and conducting copolymer of pyrrole functionalized polystyrene with pyrrole (P(PStPy-co-Py). Resulting enzyme electrodes were characterized by kinetic parameters / Vmax and Km. Behavior of enzyme electrodes upon temperature and pH changes were investigated. Glucose oxidase electrode was used for the determination of glucose in orange juice and polyphenol oxidase electrode was used for the determination of polyphenolic compounds in red wine.

In this study three different 3-ester substituted thiophene monomers were synthesized via esterification reaction of 3-thiophene ethanol with adipoyl chloride or sebacoyl chloride or octanoyl chloride in the presence of triethylamine at 00C. Characterizations of the monomers were performed by 1H-NMR, 13C-NMR, FTIR, DSC, TGA techniques. Electrochemical behavior of the monomers both in presence or absence of BFEE were studied by cyclic voltammetry. Results showed the astonishing effect of BFEE on the polymerization, where free standing films of the homopolymers could be synthesized. Copolymers of the monomers with thiophene or 3-methyl thiophene were synthesized at constant potential electrolysis and the resultant polymers were characterized by FTIR, DSC, TGA, SEM and conductivity measurements. Second part of the study was devoted to investigate the one of most interesting property of conducting polymers, the ability to switch reversibly between the two states of different optical properties, &lsquo / electrochromism&rsquo / . In recent years there has been a growing interest in application of conducting polymers in electrochromic devices. Thus, electrochromic properties of the synthesized conducting polymers were investigated by several methods like spectroelectrochemistry, kinetic and colorimetry studies. Spectroelectrochemistry experiments were performed in order to investigate key properties of conjugated polymers such as band gap, maximum absorption wavelength, the intergap states that appear upon doping and evolution of polaron and bipolaron bands. Switching time and optical contrast of the homopolymers and copolymers were evaluated via kinetic studies. Results implied the possible use of these materials in electrochromic devices due to their satisfactory electrochromic properties like short switching time and stability. Generally the homopolymers displayed color changes between yellow, green and blue colors upon variation of applied potentials. Fine tuning of the colors of the polymers were accomplished by techniques like copolymerization and lamination. These studies were supported with experiments like spectroelectrochemistry and FTIR. Results showed the possible control of the color of the electrochromic material in a predictable, controlled and reproducible manner. Yet, it was possible to achieve different tones of yellow, green, orange color in neutral state of these materials. As the last part of the study, dual type electrochromic devices based on polymers of 3-ester substituted thiophenes with poly(3,4-ethylenedioxythiophene) were constructed, where the former and the later functioned as anodically and cathodically coloring layers respectively. Spectroelectrochemistry, switching ability, stability, open circuit memory and color of the devices were investigated and the results revealed that these devices have satisfactory electrochromic parameters.

Microwave-assisted novel synthesis of poly(dibromophenylene oxide) or poly(diiodophenylene oxide) (P), conducting polymer (CP) and/or crosslinked polymer (CLP) and/or radical ion polymer (RIP) were achieved simultaneously from lithium, sodium or potassium 2,4,6-bromophenolate or sodium 2,4,6-iodophenolate in a very short time interval. Polymerizations were carried out by constant microwave energy with different time intervals varying from 1 to 20 min / or at constant time intervals with variation of microwave energy from 70 to 900 watt / or varying the water content from 0.5 to 5 ml at constant time intervals and microwave energy. Poly(dihalophenylene oxide) and radical ion polymers were characterized by FTIR (Fourier Transform Infrared), 1H-NMR (Proton Nuclear Magnetic Resonance), 13C-NMR (Carbon-13 Nuclear Magnetic Resonance), TGA/ FTIR (Thermal Gravimetric Analysis / Fourier Transform Infrared), DSC (Differential Scanning Calorimeter), SEM (Scanning Electron Microscope), ESR (Electron Spin Resonance), GPC (Gel Permeation Chromatography), UV-Vis (UV-Visible Spectroscopy), Light Scattering and Elemental Analysis. Conducting and crosslinked polymers were characterized by FTIR, TGA/ FTIR, DSC, SEM, ESR, XRD (Powder Diffraction X-Ray) and Elemental Analysis. The effects of heating time, microwave energy and water content on the percent conversion and the polymer synthesis were also investigated.

A new neutral state green polymer, poly (2,3-bis(4-tert-butylphenyl)-5,8-di(1H-pyrrol-2-yl) quinoxaline) (PTBPPQ) was synthesized and its copolymer with bis(3,4-ethylenedioxythiophene) (BiEDOT) and 4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-dodecyl-2H-benzo [1,2,3] triazole (BEBT) were produced. Finally polymers&rsquo / potential use as an electrochromic material was investigated. Electrochromic properties of the polymers were investigated by several methods including spectroelectrochemistry, kinetic and colorimetry studies. Key properties of conjugated polymers such as band gap, maximum absorption wavelength, the intergap states that appear upon doping and evolution of polaron and bipolaron bands were investigated via spectroelectrochemistry experiments. Switching times and optical contrasts of the homopolymer and the copolymer were evaluated via kinetic studies. Copolymer of TBPPQ with BiEDOT and BEBT were electrochemically synthesized and characterized. Resulting copolymer films have distinct electrochromic properties and revealed multichromism through the entire visible region. Although BiEDOT and BEBT have different oxidation potentials, the resulting copolymers have very similar redox behaviors. In a monomer free solution, both copolymers show four colors from purple, gray, light green to transmissive blue with the variation of the applied potential. Copolymerization with BiEDOT and BEBT not only decreases the band gap, Eg, but also enhances the electrochromic and optical properties. Hence, electrochemical copolymerization is considered to be a powerful tool to improve the electrochromic properties of quinoxaline derivatives. It should be noted that PTBPPQ is one of the few examples of neutral state green polymeric materials with superior switching properties. Hence, PTBPPQ can be used as a green polymeric material for display technologies.

ABSTRACT BIOACTIVE SURFACE DESIGN BASED ON CONDUCTING POLYMERS AND APPLICATIONS TO BIOSENSORS Ekiz, Fulya M. Sc., Department of Biotechnology Supervisor: Prof. Dr. Levent Toppare Co-Supervisor: Prof. Dr. Suna Timur June 2012, 88 pages An underlying idea of joining the recognition features of biological macromolecules to the sensitivity of electrochemical devices has brought the concept of biosensors as remarkable analytical tools for monitoring desired analytes in different technological areas. Over other methods, biosensors have some advantages including high selectivity, sensitivity, simplicity and this leads to solutions for some problems met in the measurement of some analytes. In this context, conducting polymers are excellent alternatives with their biocompatibility and ease of applicability for an efficient immobilization of biomolecules in preparing biosensors. Using several materials and arranging the surface properties of the electrodes, more efficient and seminal designs can be achieved. In this thesis, it is aimed to create new direct biosensors systems for the detection of several analytes such as glucose and pesticides thought to be harmful to the environment. Recently synthesized conducting polymers (polyTBT) / (poly(2-dodecyl-4,7-di(thiophen-2-yl)-2H-benzo[ d][1,2,3]triazole) and (poly(TBT 6 -NH2 ) / poly(6-(4,7-di(thiophen-2-yl)-2H-benzo[d][1,2,3]triazol-2-yl)hexan-1-amine) were utilized as a matrices for biomolecule immobilization. After successful electrochemical deposition the polymers on the graphite electrode surfaces, immobilization of glucose oxidase (GOx) and choline oxidase (ChO) were carried out. Amperometric measurements were recorded by monitoring oxygen consumption in the presence of substrates at -0.7 V. The optimized biosensors showed a very good linearity with rapid response times and low detection limits (LOD) to glucose and choline. Also, kinetic parameters, operational and storage stabilities were determined. Finally, designed biosensor systems were applied for glucose and pesticide detection in different media.

The studies reported in the thesis deal with surface modification of non-platinum metals by coating with electronically conducting polymers, namely, polyanilne (PANI) and polypyrrole (PPY). The oxidation of Г/I2, hydroquinone/quinine and [Fe(CN)6]3-/ [ Fe(CN)6]4-are studied by cyclic voltammetry and chronoamperometry experiments. It has been shown tht the redox reactions, which do not occur on bare stainless steel electrode, occur through electron-transfer mediated by conducting polymers. The effect of heating of polyaniline (PANI) at 80 0C on its electrochemical activity is studies. Although the thermogravimetric analysis indicates that PANI is stable at temperatures up to about 250 0C and it undergoes decomposition at higher temperatures, its intrinsic redox electrochemical activity decreases with duration of heating at a temperature as low as 80 0C . The polymer completely loses its electrochemical activity. The decrease in lectrochemical activity of PANI is attributed to an irreversible loss of water molecules. The reaction order for degradation of PANI is found to be close to unity, and a value of 1.63 X 10-4 s-1 is obtained for the rate constant. The deactivated PANI does not recover its electrochemical activity even after a prolonged treatment in acidic electrolytes. The electrodeposition of PANI is carried out by galvanostatic, potentiostatic and potentiodynamic methods. The impedance data reflect a marked difference between the PANI deposited by static and dynamic methods. Furthermore, the impedance parameters vary with the sweep rate used in potentiodynamic method. Electrochemical impedance spectra of the electrodes are analyzed using a transmission line model consisting of two rails of finite resistances. Electrochemical deposition of polyaniline (PANI) is carried out on a porous carbon substrate for supercapacitor studies. PANI deposited at 100 mV s-1 sweep rate by potentiodynamic technique on porous carbon substrate is found to possess superior capacitance properties. Capacitance values as high as 1600 F g-1 are obtained and PANI coated carbon electrodes facilitate charge-discharge current densities as hgh as 45 mA cm-2 (19.8 A g-1 ). Electrodes are found to be fairly stable over a long cycle-life, although there is some capacitance loss during the initial stages of cycling. Electrooxidation of ascorbic acid on polyaniline is studied in a fuel-cell. Ascorbic acid (H2A) is employed as fuel and polyaniline (PANI) as the catalyst. H2A is an environmentally and biologically friendly molecule. The catalyst, namely PANI does not consist of any platinum group metal, and at 70 0C , a maximum power density of 4.3 mW cm-2 is obtained at a current density of 15 mA cm-2 . Also, studies on anodically deposited RuO2 for capacitor applications are reported. Cathodic deposition of RuO2 generally produces a mixture of Ru and RuO2 . On the other hand, the anodic depsotion on SS substrates is found to produce RUO2 which is characterized with high power supercapacitance properties. A capacitance value of 274 F g-1 is obtained at a current density of 20mA cm-2 .

This research is focused on preparation of polypyrrole (PPy) composite particles by using socalled template oxidative polymerization method. As a template, water-soluble polymers, polymeric microgels, latex particles or bulk gels can be used. The morphology and properties of the composite particles can be controlled effectively by the proper use of the template. By choosing the dopant anion or oxidation agent it is possible to vary the conductivity of the polymer. In the case when uncrosslinked PVME was used as stabilizer, core-type polypyrrole spherical particles in the range of 50-100 nm were formed in both aqueous ethanol and water. Results of the elementary analysis, IR spectroscopy confirmed that the anionic salts can be incorporated in the PPy particles and play as the dopants. The presence of dopants in polypyrrole enhances the conductivity, especially in the case of sodium benzoate the conductivity of the final product has been improved by 3 orders. Polymeric microgels were also applied as the templates for polypyrrole deposition. When crosslinked PVME microgels were used in the oxidation polymerization of pyrrole, large PPy fibrils (appr. 400nm) were formed. Needle-like particles were formed due to the porous structure of microgels, which play a template role in the pyrrole polymerization process. When poly(VCL/AAEM) microgels were used as a template for oxidative polymerization of pyrrole, &amp;quot;raspberry-like&amp;quot; composite particles will be formed with PPy domains located in swollen hydropholic particle shell. Obtained stable composite microgels show similar thermal sensitivity as poly(VCL/AAEM) particles with fully reversible collapse-swelling properties. Increase of PPy content in composite particles increases conductivity of the composite material. The conductivity of composite particles prepared in water was much higher than that of prepared in water : ethanol mixtures. Furthermore, monodisperse PS-PEGMA particles, which were prepared in water medium by polymerization with sodium peroxydisulfate have been used as a template for deposition of polypyrrole (PPy). Obtained composite particles possess core-shell morphology where shell is composed out of small PPy nano-domains. The shell thickness can be varied by changing PPy load, controlling the overall template surface area in the system, and by influencing the pyrrole polymerization kinetics in presence of different oxidants. The last possibility provides also incorporation of different anions into polypyrrole shell. The stability of composite particles decreases gradually if the deposited PPy amount increases. It has been established that obtained particles are intrinsically coloured and the colour can be changed by the PS-PEGMA core size. Conductivity measurement shows that PS/PEGMA/PPy composite particles prepared by using phosphomolybdate as the oxidant are much more conductive than the particles prepared by the other two oxidants. The conductivity increases with the increase of PPy load in the system. Overall, the proper design of the template should give a possibility to control effectively the morphology, particle size and provide sufficient stability to the composite particles. Different morphologies, such as spherical, core-shell, raspberry and needle-like, with different particle size are expected to be available in different cases. By choosing the dopant anion or oxidation agent it is possible to vary the conductivity of the polymer. The stable water-based dispersions are expected to be used as additives for paint formulations, in electrorheology, microelectronic, ion-separation or disease diagnostics.