Thesis (Ph.D.)--University of Wollongong, 2007. / Typescript. Includes bibliographical references.

Thesis (Ph. D.)--University of Akron, Dept. of Chemistry, 2008. / "December, 2008." Title from electronic dissertation title page (viewed 12/30/2008). Advisor, Matthew Espe; Committee members, Peter Rinaldi, James Hardy, Claire Tessier, Jutta Luettmer-Strathmann; Department Chair, Kim Calvo; Dean of the College, Ronald F. Levant; Dean of the Graduate School, George R. Newkome. Includes bibliographical references.

Thesis (M.S.)--Missouri University of Science and Technology, 2010. / Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed January 6, 2010) Includes bibliographical references.

Thesis (M. Phil.)--University of Hong Kong, 2009. / Includes bibliographical references. Also available in print.

Thesis (Ph.D.) - University of St Andrews, September 2007. / Restricted until 14th September 2009.

Thesis (M.Sc.)--Memorial University of Newfoundland, 2004. / Bibliography: leaves 102-112.

Thesis (M.S.)--Rochester Institute of Technology, 2005. / Typescript. Includes bibliographical references (leaves 89-94).

Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xv, 192 p.; also includes graphics (some col.). Includes bibliographical references (p. 183-192). Available online via OhioLINK's ETD Center

>Magister Scientiae - MSc / Applications of electrochemiluminescent conjugated polymers offer promising solutions in addressing the problem of light emitting devices. However, the challenging problems that hamper their application in light emitting devices are loss of signal due to diffusion of the electrochemiluminescence (ECL) reagent out of the detection zone, limited ability to repeatedly cycle an individual luminophore and high reagent consumption. In this work, the main objective was to produce conducting polymers with enhanced electrochemiluminescence by tuning the properties of the polymer itself. The electrochemical and photophysical properties of films of polyaniline (PANI) and poly(8-anilino-1- naphthalene sulfonic acids) (PANSA) synthesized through electro- and chemical polymerization methods were also investigated. The electrosynthesis of PANSA undoped and doped with anthracene sulfonic acid (ASA), 1,2-naphthaquinone-4-sulfonic acid (NSA) and carbon nanotubes (CNT) in acid medium was investigated and the cyclic voltammograms (CV) showed the growth of the polymer during polymerization. The CV multiscan characterization displayed that the growth of the polymer was dependent of the scan rate and the three redox couples were observed as indicative of the three redox states of typical polyaniline and its derivatives. The results also showed that the peak currents were diffusion controlled and the electron charge transport coefficient (De) of the electrosynthesized polymers was found to range between 10⁻⁸ and 10⁻⁹ cm² s⁻¹ for PANSA, PANSA-ASA, PANSA-NSA and PANSA-CNT. The De value indicates that the movement of electrons along the polymer chain was averagely fast. The transmission electron microscopy (TEM) was used to investigate the electronic morphology of the polymers and the TEM images showed an intertwinement of tubings which aggregate into a ring with a mixture of tubings and plastic sheets. The chemical synthesis of PANI, PANSA and PANI-NSA was carried out by using monomers analine, 8-anilino-1-naphthalene sulfonic acid, and aniline with 1,2- naphthaquinone-4-sulfonic acid, respectively, using oxidants. All chemically synthesized polymers exhibited quinoid and benzoid bands typically see in polyaniline FTIR and Raman spectra confirmed the successfully formation of polymers. The CV characterization of these polymers showed distinctive redox peaks. This proved that the polymers were electroactive, conductive and exhibited reversible electrochemistry. The De of the electrosynthesized polymers was found to be ~10⁻⁵ cm² s⁻¹ for chemically synthesized polymers. The electric conductivity measurement showed to increase from 10⁻⁴ to 10⁻² when aniline was polymerized with NSA dopant, this might be related to the process of electron transfer from dopant to polymer. Scanning electron microscopy for external morphology showed that the polymers were made of different nano- rods polymeric structures. Photophysical properties of electro- and chemically synthesized PANSA and PANI were investigated through UV-vis absorption, fluorescence behaviour, and lifetime. The UV-vis absorption spectra of these polymers showed that they exhibited absorption bands corresponding to the polyemeraldine redox state of typical polyaniline. The effect of dopants resulted in the increase in solubility of the polymers with a small shift of absorption bands due to incorporation of dopants in to the backbone of the polymer. The fluorescence emission spectra of the electrochemically synthesized PANSA with and without dopants were observed to be similar and mirror image of the excitation spectra and corresponding to the electronic band of the benzoid ring in the polyemeraldine form confirming that the fluorescing molecule in these polymers were the benzoid rings. However, the emission spectra of the chemically synthesized PANSA and PANI were different to excitation spectra due to loss of symmetry upon excitation. The effects of chemically synthesized PANI, PANSA and PANI-NSA addition on the photophysical properties of [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂) were investigated in order to understand the interaction of polymer and [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂. The analysis revealed that the presence of polyaniline and its derivatives enhanced the [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)2 absorption band, photoluminescence and fluorescence lifetime. The enhancement observed from interaction of [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂ with polyaniline and its derivatives might be due to the excited state electron transfer from the PANI and PANSA excited state to the [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂. It was further demonstrated in this work that it is possible to form polyaniline and PANSA doped with [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂ films on ITO electrode using potentiostatic growth method to favour ECL production. The results showed that all films generated ECL in the presence of Tripropylamine (TPA) as a co-reactant and their emission properties depend on time used to prepare the film. The enhancement of ECL signal was due to a positive electron transfer from the conducting polymer (PANI and PANSA) to [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂ complex. The results highlighted the potential of these polymeric luminophores usage in the manufacturing of the ECL devices.

The aim of this study is the production of a nanofibrous electroactive mat and the investigation of its potential use in tissue engineering, and more specifically for wound dressing purposes. The limitations regarding electrospinnability of the conducting polymer will be identified and addressed and the factors related to its biological properties will be evaluated. To this end, conducting polymer, polyaniline (PANI) was chosen as the electroactive component and blend electrospinning was identified as the most suitable method to produce continuous nanofibres containing PANI. Various biocompatible polymers and solvent systems were investigated for their suitability to assist in electrospinning and PEO (polyethylene oxide) and CH (chitosan) were chosen as carrier polymers for blend electrospinning of PANI. Consequently, CSA (Camphor-10-sulfonic acid (β)) doped PANI/PEO and CSA doped PANI/CH conducting nanofibrous mats were produced by electrospinning. The electrospinning windows for both blends were determined by using full factorial experimental designs. The combined effects of the humidity, voltage and flow rate on the fibre morphology and diameter were examined for both blends, demonstrating that the ambient humidity is the critical factor affecting the electrospinning process and determining the electrospinning window for a conducting polymer. Low humidity favors the formation of defect free fibres while high humidity either hinders fibre formation or causes the formation of defects on the fibres. In the case of PANI/PEO blends, different levels of PANI doping were investigated, and high level of doping with CSA was found to lead to the formation of crystalline structures. Data fitting was used to explore the behavior of conducting polymers using the case of PANI/PEO electrospinning and very good agreement between experimental and theoretical predictions was obtained for only a limited range of experimental conditions, whereas deviation was observed for all other sets of conditions. In the case of PANI/CH, the effect of different ratios of conducting polymer in the blend (0:1, 1:3, 3:5 and 1:1) was examined, as for the electrospinnability, resulting 3 nanofibrous morphology, mat contact angle, electrical conductivity, antibacterial activity and cellular biocompatibility. The incorporation of PANI in the electrospinning blend, affected the electrospinnability of the solution, making it more susceptible to RH deviations, and contributed to the decrease of nanofibre diameter. Higher PANI content was found to result in more hydrophobic and more conducting mats. The method that was used to stabilize the PANI/CH mats was also found to affect antibacterial activity and conductivity. The produced blend mats, exhibited antibacterial activity which was higher against Gram positive B. subtilis and lower against gram negative E. coli. The cellular biocompatibility was assessed with human osteoblasts and fibroblasts, in terms of cell proliferation rate as well as cell attachment and morphology. Cells of both cell lines adhered well and showed good growth rates on nanofibrous substrates of all blend ratios when compared to standard tissue culture plastic. Finally, amongst the PANI containing mats, the one of 1:3 PANI:CH ratio, was identified as the best to support osteoblast and fibroblast cell proliferation when compared to the pure chitosan.