Filmes de politiofeno foram eletroquimicamente depositados em diversos substratos eletródicos em meio aquoso fortemente ácido e as características dos materiais formados foram estudadas através de técnicas voltamétricas, espectroscópicas (FTIR e UV-Vis. e raios X) e por microscopia eletrônica de varredura. As propriedades foram comparadas com as de filmes sintetizados em meio não-aquoso concluindo-se que o material produzido em meio aquoso mostra-se mais adequado para a aplicação como suporte de partículas eletrocatalisadoras, por sua maior atividade eletroquímica, homogeneidade e estabilidade. Foram então incorporadas partículas de Pd e Pt que foram investigadas quanto a ação catalítica frente as reações de oxidação de hidrogênio (ROH) e redução de oxigênio (RRO) em ácido sulfúrico 2,0 M. Os materiais produzidos foram primeiramente caracterizados através de técnica de absorção de raios X, tendo sido observada a formação de aglomerados de partículas bastante pequenas que não alteram seu estado de oxidação com a mudança do potencial eletródico. Verificou-se que ambos os catalisadores apresentam uma certa atividade inicial frente a ROH, mas o desempenho não é estável devido à ocorrência de processos degradativos da cadeia polimérica. Por outro lado, observou-se que os filmes contendo Pt apresentam elevada atividade catalítica frente a RRO, substancialmente maior que a de filmes contendo Pd. O mecanismo da reação mostrou-se dependente da natureza do catalisador, sendo também influenciado pelo contato com o filme polimérico. Para a Pt em contato direto com o eletrólito, a reação ocorre com envolvimento de 4 elétrons e com formação de água como produto final. Para o caso em que as partículas de Pt são recobertas por politiofeno, verifica-se a participação do peróxido de hidrogênio como intermediário, sendo que somente uma certa fração do mesmo reduz-se para formar água. No caso do Pd, o processo leva à formação de peróxido de hidrogênio em baixos sobrepotenciais, que depois é reduzido, com formação de água, em sobrepotenciais mais elevados. / Polythiophene films were electrochemically grown on several electrode substrates from strong acid aqueous solutions, and the characteristics of the materials investigated using cyclic voltammetry, FTIR and UV-Vis spectroscopies, and scanning electron microscopy. Compared to the materials prepared in non-aqueous media, the polymer synthesized in aqueous media shows more adequate characteristics for using as support for electrocatalytic particles, because of its higher electrochemical activity and stability, and bulk homogeneity. Particles of Pd and Pt were electrochemically incorporated on these polymer films, and the electrocatalytic properties of such composites investigated with respect to the hydrogen oxidation (HOR) and oxygen reduction (ORR) reactions in 2.0 M sulfuric acid solutions. Previously to these kinetic studies, the composites were characterized using X-ray absorption spectroscopy from which it is seen that the catalysts are deposited as agglomerates composed of very small particles whose oxidation states are not changed by changing the electrode potential. Both catalysts present some initial activity for the HOR, but the performance is not stable due to the occurrence of a degradation process involving the polymer chain. On the other hand, it is observed that the films containing Pt show an enhanced catalytic activity for the ORR which is considerably higher than of that containing Pd. The reaction mechanism is dependent on the catalyst nature and also influenced by the contact with a polymer film coating. For Pt in direct contact with the supporting electrolyte, the reaction occurs involving 4 electrons leading to water as final product. For Pt particles covered with a polymer layer, participation of hydrogen peroxide seems to be important with only a fraction of this specie being reduced to water. In the case of Pd, the process involves formation of hydrogen peroxide at low overpotentials, which is then reduced to water at higher overpotentials.

Please read the abstract in the section front of this document. / Dissertation (MSc (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

Despite the poor understanding of charge transfer in conducting polymers, conducting-polymer-based devices have achieved considerable commercial success. This success is based largely on the reproducibility of the measurable properties. It is the purpose of this study to further clarify charge transfer characteristics of conducting polymers under varying conditions. We studied a conducting polymer called polyaniline. Polyaniline was available in its doped conducting form called emeraldine salt and in its undoped form called emeraldine base. Three types of polyaniline were studies, electrosynthesized (doped by HCI), chemically synthesized (doped by HCI) and commercial polyaniline obtained from Adlrich Company and doped by camphor sulfonic acid. Initially we investigated whether charge transfer was ionic or electronic by observing the change in resistance with time for a fixed applied current. It was concluded that condition in this material is electronic. Electrical measurements were obtained using the four-point probe and the Montgomery methods. The samples investigated were in pellet and film forms. We investigated charge transfer over the temperature regime 30-450 K by applying the following methods: scanning electron microscopy to investigate the surfaces of pellet and film samples, Fourier transform infrared spectroscopy and Raman spectroscopy to investigate the effect of annealing on the molecular structure of the polymer and thermal analysis to investigate the loss of substances from the polymer as a result of the annealing process. The conductivity of the material was also analyzed over the entire temperature regime. The following were observed: • Conductivity in polyaniline is governed my monomer units. • The decrease in conductivity with increase annealing temperature is related to moisture loss, loss of dopant ions and polymer degradation. • The variable range hopping model in three dimensions, satisfactorily describes charge transfer mechanism in polyaniline. • Conductivity in polyaniline is temperature activated. • Conductivity varies with position on the sample surface. • The effect of pellet pressing pressure to conductivity is negligible. • Current-voltage characteristics for polyaniline exhibit non-ohmic behavior at high current values, (>0.2 mA for T <80 K), applied between the current probes of a four-point probe measuring instrument. / Dissertation (MSc (Physics))--University of Pretoria, 2006. / Physics / unrestricted

Derivados do politiofeno são promissores para obtenção de sensores ópticos devido as suas propriedades crômicas, enquanto que polímeros azosubstituídos (azopolímeros) têm sido estudados para várias aplicações, tal como memórias ópticas. Neste trabalho procurou-se unir as propriedades dos derivados politiofênicos as dos azopolímeros através da preparação de um polímero tiofênico azosubstituído, obtido pela funcionalização do monômero tiofênico com um grupo azobenzênico. Para fins de comparação, foram também sintetizados um derivado polialquiltiofeno, o poli(3-octiltiofeno), e um copolímero formado a partir da união dos monômeros 3- octiltiofeno e do tiofeno azosubstituído. A obtenção do monômero azosubstituído foi feita a partir de uma reação de esterificação entre o ácido 3-tiofeno acético e o corante comercial vermelho disperso 1 (disperse red 1, DR1), ao passo que o monômero alquilado foi adquirido comercialmente. Os polímeros foram sintetizados por polimerização oxidativa com cloreto fénico e caracterizados químicoestruturalmente pelas técnicas de FTIR, 1H RMN, análise elementar, HPSEC e análise térmica (TG e DSC). Dessas análises comprovou-se a formação dos homopolímeros, mas não foi possível confirmar a formação do copolímero e ainda para esse caso, obteve-se uma menor quantidade de unidades azosubstituídas do que a pretendida. A análise da fotoluminescência destes materiais mostrou a influência do tipo de cadeia lateral na intensidade e no formato do espectro de emissão desses polímeros. A espectroscopia de UV-Vis foi utilizada para o estudo de suas propriedades crômicas, sendo observada a presença de termo- e solvatocromismo. O termocromismo foi analisado em solução e na forma de filmes e o solvatocromismo em soluções de solventes puros e em misturas de THF/ n-hexano com diferentes proporções. Esses polímeros também apresentaram alterações em seus espectros de absorção como resposta à variação do pH da solução. A birrefringência fotoinduzida, técnica de estudo visando a aplicação dos polímeros em memórias ópticas, somente foi observada para o homopolímero azosubstituído. Os resultados obtidos neste trabalho indicam que o politiofeno azosubstituído é um candidato promissor para elemento ativo em uma série de aplicações, tais como sensores de diversos tipos e em dispositivos de marcação oculta / Polythiophene derivatives are promising for optical sensors due to their chromic properties while azofunctionalized polymers have been used in several applications such as optical memories. In this work, an azosubstituted polythiophene was prepared by the functionalization of the thiophenic monomer with an azobenzene moiety in order to combine the polythiophene properties with those from the azopolymers. For the sake of comparison, a polyalkylthiophene, the poly(3- octylthiophene), and a copolymer of 3-octylthiophene and the azothiophene were synthesized. The azosubstituted monomer was synthesized by the esterification reaction of 3-thiopheneacetic acid and the commercial dye Disperse Red 1 (DRI), whilc the alkyl thiophene monomer was purchased. The polymers were prepared by oxidative polymerization reactions with ferric chloride and characterized chemically and structurally using FTIR, 1H NMR, elemental analysis and thermal analysis (TG and DSC) techniques. From these analyses, the formation of homopolymers was confirmed, but it was not possible to confirm the formation of the copolymer. In the latter, the amount of azosubstituted units was smaller than expected. The analysis of the polymers photoluminescence showed the influence of the side chain in the intensity and shape of the emission spectra. UV-Vis spectroscopy was used to study the polymer chromic properties which showed thermo- and solvatochromism. Thermochromism was analyzed in solution and in thin solid films and the solvatochromism was studied in pure solvent solutions and mixtures of THF/hexane in different ratios. These polymers also had their absorption spectra affected by changing the concentration of a protonic acid (HCI) solution. Photoinduced birefringence, aiming at optical memories applications, was only observed for the azosubstituted homopolymer. The overall results indicate that the azosubstituted polythiophene is promising as active material for several applications, such as different types of sensors and security-labeling devices

Conductors with IR (infrared) plasma frequencies are potentially useful hosts of surface plasmon polaritons (SPPs) with subwavelength mode confinement for sensing applications. The underlying aim of this work is to identify such conductors that also have sharp SPP excitation resonances for biosensor applications at infrared (3-11 m) wavelengths, where biological analytes are strongly differentiated by their IR absorption spectra. In this work, various materials were investigated such as a heavily doped semiconductor, a semimetal, a conducting polymer and its composite. Heavily doped silicon was investigated by tuning its plasma frequency to the infrared region by heavily doping. The measured complex permittivity spectra for p-type silicon with a carrier concentration of 6  1019 and 6  1020 cm -3 show that these materials support SPPs beyond 11 and 6 m wavelengths, respectively. SPP generation was observed in angular reflection spectra of doped-silicon gratings. Photon-to-plasmon coupling resonances, a necessary condition for sensing, were demonstrated near 10 m wavelength for the heaviest doped, and the observed resonances were confirmed theoretically using analytic calculations. The permittivity spectra were also used to calculate SPP mode heights above the silicon surface and SPP propagation lengths. Reasonable merit criteria applied to these quantities suggest that only the heaviest doped material has sensor potential, and then mainly within the wavelength range of 6 to 10 m. iv The semimetal bismuth (Bi) has an infrared plasmon frequency less than the infrared plasma frequency of noble metals such as gold and silver, which is one order of magnitude lower than their plasma frequencies. The excitation of IR surface plasmons on Bi lamellar gratings in the wavelength range of 3.4 µm to 10.6 µm was observed. Distinct SPP resonances were observed although the usual condition for bound SPP is not satisfied in this wavelength range because the real part of the permittivity is positive. The excitation of these resonances agrees theoretically with the electromagnetic surface waves called surface polaritons (SPs). The measured permittivity spectra were used to calculate the SP mode heights above the bismuth surface and SP propagation length, which satisfied our criteria for sensors. A conducting polymer and its composite with graphite were also investigated since their plasma frequency may lie in the infrared region. Polyaniline was chemically synthesized and doped with various acids to prepare its salt form. A composite material of polyaniline with colloidal and nano-graphite was also prepared. Optical constants were measured in the long wave infrared region (LWIR) and were used to calculate SPP propagation length and penetration depth. SPP resonance spectra were calculated and suggested that polyaniline and its composite can be used as a host with sufficient mode confinement for IR sensor application.

No description available.

No description available.

Long-distance radical cation transport was studied in DNA condensates where linearized pUC19 plasmid was ligated to an oligomer and transformed into DNA condensates with spermidine. DNA condensates were detected by Dynamic Light Scattering and observed by Transmission Electron Microscopy. Introduction of charge into the condensates causes long-distance charge migration, which is detected by reaction at the remote guanines. The efficiency of charge migration in the condensate is significantly less than it is for the corresponding oligomer in solution. This result is attributed to a lower mobility for the migrating radical cation in the condensate, caused by inhibited formation of charge-transfer-effective states. Radical cation transport was also studied in DNA condensates made from an oligomer sandwiched between two linearized plasmids by double ligation. Unlike the single ligated plasmid condensates, the efficiency of charge migration in the double ligated plasmid-condensates is high, indicative of local structural and conformational transformation of the DNA duplexes. Organic monomer units having extended ð-conjugation as part of a long conducting polymer was synthesized and characterized. The monomer units were covalently attached to particular positions in DNA oligonucleotides by either the convertible nucleotide approach or by phosphoramidite chemistry. Successful attachment of the monomer units to DNA were confirmed by mass spectral analysis. The DNA-conjoined monomer units can self assemble in the presence of complementary sequences which act as templates that can control polymer formation and structure. By this method the para-direction of the polymer formation can be enforced and may be used to generate materials having nonrecurring, irregular structures.

The overall objective of this work was to assess the suitability of poly(3-octylthiophene) (P3OT) to sustain MC3T3-E1 osteoblast attachment and growth. The central hypothesis was that specific P3OT film properties (i.e., thickness, film preparation conditions, and level of doping) are able to regulate osteoblast functions (i.e., attachment and proliferation). Discrete and combinatorial techniques were utilized to prepare and characterize thin films of P3OT, a semiconductor in its undoped state, and to study its interaction with MC3T3-E1 osteoblasts. In this work we demonstrate that P3OT is a suitable surface to sustain MC3T3-E1 attachment and proliferation with no observed cytotoxicity. We show that P3OT has an effect on MC3T3-E1 attachment and proliferation as area, circularity, and proliferation ratio are significantly different for P3OT compared to control surfaces. We also demonstrate that P3OT doping and film preparation conditions have an effect on osteoblast attachment and proliferation but that thickness over a low and high range does not affect osteoblast functions. This work is significant because it contributes to the growing area of conducting polymers in biomedical applications and establishes P3OT as a potential cell substrate that sustains MC3T3-E1 attachment and promotes high levels of cell proliferation.

Described herein are three projects centered on the synthesis of conducting polymer derivatives for various applications. The first is the novel synthesis of 9,9-dioctylfluorene-co-benzothiadiazole [F8BT] oligomers through solid phase synthesis for the study of the thermodynamics and kinetics of electron transfer in the polymer. The second endeavor involves the synthesis of a series of 4”,3’’’-dialkyl-2,2’:5’,2”:5”,2’’’:5’’’,2’’’’:5’’’’,2’’’’’-sexithiophenes for the studies on crystal packing and surface deposition of organic p-type semiconducting materials. Lastly is described the development of a conducting metallopolymer based on the ligand 2,6-Bis(4-(2,2’-bithiophen-5-yl)-1H-pyrazol-1-yl)pyridine for use in a drug delivery system. / text