In this research, a series of synthetically engineered copolymers were synthesized containing polysaccharides (e.g., β-cyclodextrin and chitosan) to address the removal of trihalomethanes (THMs) from water environments. There are two main parts in this research thesis: i) the preparation and characterization of polysaccharide-based copolymers; ii) sorption studies of the copolymers with chloroform and total THMs (TTHMs) in aqueous solution. In the first part of this thesis, grafted polyester, polyester and grafted polyamide copolymers were prepared by cross-linking β-cyclodextrin (β-CD) and chitosan (CS) with various cross-linkers, including poly (acrylic acid) (PAA), terephthaloyl (TCl), and sebacoyl chloride (SCl), respectively. The synthesized copolymer materials were characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA), Differential scanning calorimetry (DSC), elemental (C and H) analyses, and NMR spectroscopy. Nitrogen porosimetry was used to analyze the surface area and pore structure characteristics of the copolymers and starting materials in solid state. The sorption properties of the copolymers in aqueous solution were studied using different dye probes (e.g., p-nitrophenol and methylene blue) by UV–Vis spectrophotometry. The copolymers showed markedly varied interactions with dye probes in accordance with their composition, surface area, and pore structure characteristics. Diverse materials were afforded by variation of the synthetic conditions. The sorption isotherms were evaluated with various isotherm models (e.g., Langmuir, BET, Freundlich and Sips). The Sips isotherm showed the best overall agreement with the experimental results and the sorption parameters provided estimates of the sorbent surface area and the sorption capacity for various copolymers in aqueous solution. The copolymer sorbents display tunable physicochemical properties according to the synthetic conditions. In the second part of this thesis, the direct aqueous injection (DAI) method with gas chromatography (GC) with electron capture or electrolytic conductivity detectors (ECD) enabled quantitative detection of chloroform and TTHMs in water. A preliminary adsorption study and kinetic study of chloroform provided the information to establish the experimental protocol for the sorption study. The sorption parameters were evaluated using the Sips model. The sorption capacity (Qm) values of chloroform for these synthetically engineered copolymers at similar conditions ranged from 0.00335-1.70 mmol/g. The relative ordering of the Qm values was observed: β-CD/PAA 1:5 > SCl-5 > SCl-10 ~ CP-1 > β-CD/PAA 1:10 > CP-5 > AC > β-CD/PAA 1:5 at high mixing speed. An extension of the sorption study for copolymers toward the multi-component THMs in water was carried out. The copolymers showed distinct adsorption capacities to THMs: chloroform (0.0485-0.287 mmol/g); DBCM (0.0712-0.277 mmol/g); BDCM (0.0684-0.387mmol/g); and bromoform (0.0522-1.07 mmol/g). The copolymers exhibited relatively high selectivity toward individual components of THMs due to their variable molecular size and polarizability. The copolymers showed favorable adsorption (e.g., β-CD/PAA 1:5, CP-1) and each type of polysaccharide (e.g., β-CD and CS) copolymers displays great potential for the removal of halomethane-based contaminants.

Master of Science / Department of Physics / Robert Szoszkiewicz / Nanoscale modifications of polymer surfaces by scratching them with sharp tips with curvature radii of tens of nanometers and at variable temperatures are expected to provide wealth of information characterizing wear response of these polymers. Such studies are important in the light of understanding the nanoscale behavior of matter for future applications in advanced polymer coatings. This thesis describes how Atomic Force Microscopy (AFM) and hot-tip AFM (HT-AFM) methods were used to characterize thermal and mechanical properties of a 30 nm thick film of poly(styrene-block-ethylene oxide), PS-b-PEO, and modify its lamellar surface patterns. Additionally, it is revealed how contact AFM and HT-AFM methods can efficiently characterize the wear response of two popular polymer surfaces, poly(methyl methacrylate), PMMA, and polystyrene, PS. The AFM and HT-AFM studies on PS-b-PEO copolymer were aimed at producing spatial alignment of respective PS and PEO parts. Instead, however, surface ripples were obtained. These measurements are explained using mode I crack propagation model and stick-and-slip behavior of an AFM tip. In addition, HT-AFM studies allowed extraction of several thermo-physical properties of a PS-b-PEO film at local volumes containing about 30 attograms of a polymer. These thermo-physical quantities are: PEO melting enthalpy of, 111 ± 88 J g[superscript]-1, PS-b-PEO local specific heat of 3.6 ± 2.7 J g[superscript]-1K[superscript]-1, and molecular free energy of Helmholtz of 10[superscript]-20 J nm[superscript]-2 for the PEO within PS-b-PEO. Utilizing a spiral scan pattern at constant angular speed and at various temperatures at the AFM tip-polymer interfaces, the wear response of PS and PMMA polymers was characterized. Cross-sections along the obtained spiral wear patterns provided plots of polymer corrugation as a function of scanning speed. From these studies it was found that the corrugation of the modified polymer surface decays exponentially with linear velocity of the scanning tip.

O reparo de falhas ósseas tem sido motivo de preocupação e estudos em ortopedia. O enxerto esponjoso autógeno é consagrado e definido como padrão ouro, porém, o leito doador é limitado e a colheita pode causar grande morbidade. Tem sido proposto, ao longo dos anos, o uso de materiais naturais, sintéticos e fatores de crescimento com resultados promissores. O desenvolvimento de membranas e matrizes tridimensionais, baseado em biomateriais reabsorvíveis e biocompatíveis, tem demandado estudos voltados à síntese e avaliação. O objetivo do estudo foi avaliar o processo de reparação óssea por meio do uso de três polímeros bioativos em falhas ósseas em tíbias de coelhos. Foram estudados 48 coelhos machos, adultos jovens, distribuídos em quatro tempos experimentais (três, sete, 14 e 30 dias). Cada tíbia constituiu uma unidade experimental, de modo que foram confeccionados dois defeitos ósseos monocorticais em região proximal medial de cada tíbia. Cada tempo experimental contemplou quatro grupos: controle - sem adição de biomaterial; M1 - orifícios protegidos com Poli L Lactide co Policaprolactone / Poli Glicol Etilênico; M2 - Poli L Lactide co Policaprolactone / Poli Glicol Etilênico / Fosfato Tricálcico e M3 - Poli L Lactide co Policaprolactone / Poli Glicol Etilênico / nano Hidroxiapatita. Ao final de cada período os indivíduos foram submetidos à eutanásia e obtidos cortes histológicos das tíbias, corados com técnica de HE, TRAP e Masson. Foram feitas análises histomorfológicas descritivas e histomorfométricas, com mensuração do tecido ósseo neoformado, porcentagem da área de trabéculas ósseas, número de osteoclastos e porcentagem de trabéculas ósseas com osteoclastos. Os dados foram submetidos aos testes de Kruskal-Wallis e Mann-Whitney. Os resultados mostraram absorção incompleta da membrana e ausência de toxicidade. Para os períodos de 14 e 30 dias, o grupo controle exibiu matriz óssea no interior do defeito e nos grupos M1, M2 e M3, o calo ósseo formou-se no interior e em grande quantidade na superfície do defeito e no periósteo. Aos 30 dias, o grupo controle exibiu calo ósseo com maturação mais avançada que nos grupos com membranas. Aos 14 e 30 dias, a área de calo ósseo do grupo controle foi significativamente menor em relação aos grupos com membranas (p=0,001 e p=0,003 respectivamente). As lâminas dos grupos com membranas exibiram sinais de remodelação ativa tanto aos 14 como aos 30 dias, denotando o potencial osteoindutor e osteocondutor destes biomateriais. Aos 14 dias a neoformação óssea no grupo M3 (com nano-HA) foi superior ao M2 (com -TCP), o que pode indicar que o potencial osteoindutor e osteocondutor do material M3 foi superior ao M2 nesta fase da reparação. Os resultados permitiram concluir que apesar dos biomateriais testados no experimento estimularem a neoformação óssea, a remodelação foi mais tardia. / Bone gap repairs are a major concern in orthopedics. Autologous cancelous bone graft is considered the golden standard technique, but donation site is limited and its grafting is related to greater morbidity. The use of natural and synthetic materials, as well as growth factors, has been proposed with promising outcomes. The development of membranes and tridimensional matrixes based in reabsorbable and biocompatible materials require more studies targeting their synthesis and evaluation. The aim of the present study was to evaluate the bone repair process using three osteoinductive polymers in circular bone gaps in rabbit\'s tibias. Fourty eight young adult male rabbits were divided into four experimental moments (three, seven, fourteen and thirty days). Each tibia was considered one experimental unit, in which two monocortical bone defects were made in the proximal medial region of the bone. Each experimental time was used in the following four groups: control - without biomaterial; M1 - defects protected with Poli L Lactide co Policaprolactone / Poly Ethylene Glycol; M2 - Poli L Lactide co Policaprolactone / Poly Ethylene Glycol / Tricalcium Phosphate and M3 - Poli L Lactide co Policaprolactone / Poly Ethylene Glycol / Hydroxyapatite. At the end of each period the animals were euthanized and histological sections were stained with HE, TRAP and Masson techniques. Histomorphologic and histomorphometric analysis were made and consisted in the measuring of new bone tissue formation, percentage of trabecular area, number of osteoclast and percentage of trabeculae with osteoclasts. Data were analyzed with Kruskal-Wallis and Mann-Whitney test. Results showed an incomplete absortion and no toxicity of membranes. At 14 and 30 days, control group showed bone callus in the defect, and groups M1, M2 and M3 showed bone callus in the defect and around the surface of the defect. At 30 days, the control group showed bone callus in a more mature phase in comparison to the groups with membranes. At 14 and 30 days, the bone callus area in the control group (p=0.001) was significantly smaller than the membrane groups (p=0.003). The groups with membranes exhibited signs of active remodeling at 14 and 30 days, demonstrating that the biomaterials have greater osteoinduction and osteoconduction potential. At 14 days, we found more bone formation in group M3 (nano-HA) relative to group M2 (-TCP), which may indicate that the osteoinductive / osteoconductive potentials of M3 in this bone repair phase was superior in relation to M2. The biomaterials tested in the study stimulate bone formation, but caused delayed in bone remodeling.

Nesta tese, estudamos a eletrossíntese de polímeros conjugados eletroluminescentes no azul. Filmes de poli(p-fenileno) (PPP), co-poli(p-fenileno-pirrol) (CPPI) e co-poli(p-fenileno-3-metiltiofeno) (CFMET) foram preparados por voltametria cíclica em eletrodos de vidro condutor (ITO) em uma solução não-aquosa de acetonitrila e perclorato de tetrabutilamônio contendo os monômeros e pares de co-monômeros a diferentes concentrações. Durante a síntese dos filmes de PPP, CPPI e CP3MET, a célula eletroquímica foi posicionada dentro de uma caixa seca contendo CaCl2 como agente secante e em atmosfera de N2(g) super-seco com o objetivo de reduzir a umidade do ar no meio de síntese. A baixa umidade do ar obtida durante as medidas permitiu o controle de parâmetros de crescimento dos filmes de PPP e de seus derivados (CPPI e CP3MET). A morfologia dos filmes foi correlacionada aos seus valores de espessura e de rugosidade obtidos por microscopia de força atômica (AFM). As propriedades ópticas dos filmes foram também investigadas por espectroscopia no UV-VSNIR em função do número de ciclos da varredura obtidos durante a eletrossíntese. As respostas eletroquímicas, dos filmes de FPP, CPPI e CP3MET foram obtidas por voltametria cíclica em uma solução livre de monômero. Estes filmes tiveram ainda a confirmação de suas estruturas químicas por meio de resultados obtidos por espectroscopia no infravermelho (FTIR) e por microespectroscopia e mapeamento Raman / This work describes the electrochemical synthesis of poly(p-phenylene) (PPP), p-phenylene-pyrrole copolynier (GPPIC) and p-phenylene-3methylthiophene copolymer (CP3MET). The main interest in studying these materials comes from its blue-electroluminescent properties, which make them suitable for application in electroluminescent devices. The polymerization was carried out using cyclic voltammetry in an acetonitrile non-aqueous medium containing tetrabutylammonium perchlorate and different concentration of each monomer. All the films were synthesized onto indium-tin-oxide covered glass (EO) electrodes. In order to enhance the film quality, electropolymerization was carried out within a glove box containing CaCl2, which was added as a drying agent, and under N2 atmosphere. The low amount humidity during the measurements allowed us to correlate the morphological, electrochemical and optical properties of the films of PPP and derivatives (CPPI and CP3MET). The optical properties of the films were investigated by UV-VIS-NIR spectroscopy after varying the number of cyclos reached during the preparation of the films. The electrochemical response of the films was analyzed via cyclic voltammetry using a monomer-free electrolytic solution. The morphology of the films was correlated to their values of thickness and roughness as obtained by using atomic force microscopy (AFM) and the structural characterization of PPP e their derivatives were obtained by micro-Raman spectroscopy and Raman mapping.

O reparo de falhas ósseas tem sido motivo de preocupação e estudos em ortopedia. O enxerto esponjoso autógeno é consagrado e definido como padrão ouro, porém, o leito doador é limitado e a colheita pode causar grande morbidade. Tem sido proposto, ao longo dos anos, o uso de materiais naturais, sintéticos e fatores de crescimento com resultados promissores. O desenvolvimento de membranas e matrizes tridimensionais, baseado em biomateriais reabsorvíveis e biocompatíveis, tem demandado estudos voltados à síntese e avaliação. O objetivo do estudo foi avaliar o processo de reparação óssea por meio do uso de três polímeros bioativos em falhas ósseas em tíbias de coelhos. Foram estudados 48 coelhos machos, adultos jovens, distribuídos em quatro tempos experimentais (três, sete, 14 e 30 dias). Cada tíbia constituiu uma unidade experimental, de modo que foram confeccionados dois defeitos ósseos monocorticais em região proximal medial de cada tíbia. Cada tempo experimental contemplou quatro grupos: controle - sem adição de biomaterial; M1 - orifícios protegidos com Poli L Lactide co Policaprolactone / Poli Glicol Etilênico; M2 - Poli L Lactide co Policaprolactone / Poli Glicol Etilênico / Fosfato Tricálcico e M3 - Poli L Lactide co Policaprolactone / Poli Glicol Etilênico / nano Hidroxiapatita. Ao final de cada período os indivíduos foram submetidos à eutanásia e obtidos cortes histológicos das tíbias, corados com técnica de HE, TRAP e Masson. Foram feitas análises histomorfológicas descritivas e histomorfométricas, com mensuração do tecido ósseo neoformado, porcentagem da área de trabéculas ósseas, número de osteoclastos e porcentagem de trabéculas ósseas com osteoclastos. Os dados foram submetidos aos testes de Kruskal-Wallis e Mann-Whitney. Os resultados mostraram absorção incompleta da membrana e ausência de toxicidade. Para os períodos de 14 e 30 dias, o grupo controle exibiu matriz óssea no interior do defeito e nos grupos M1, M2 e M3, o calo ósseo formou-se no interior e em grande quantidade na superfície do defeito e no periósteo. Aos 30 dias, o grupo controle exibiu calo ósseo com maturação mais avançada que nos grupos com membranas. Aos 14 e 30 dias, a área de calo ósseo do grupo controle foi significativamente menor em relação aos grupos com membranas (p=0,001 e p=0,003 respectivamente). As lâminas dos grupos com membranas exibiram sinais de remodelação ativa tanto aos 14 como aos 30 dias, denotando o potencial osteoindutor e osteocondutor destes biomateriais. Aos 14 dias a neoformação óssea no grupo M3 (com nano-HA) foi superior ao M2 (com -TCP), o que pode indicar que o potencial osteoindutor e osteocondutor do material M3 foi superior ao M2 nesta fase da reparação. Os resultados permitiram concluir que apesar dos biomateriais testados no experimento estimularem a neoformação óssea, a remodelação foi mais tardia. / Bone gap repairs are a major concern in orthopedics. Autologous cancelous bone graft is considered the golden standard technique, but donation site is limited and its grafting is related to greater morbidity. The use of natural and synthetic materials, as well as growth factors, has been proposed with promising outcomes. The development of membranes and tridimensional matrixes based in reabsorbable and biocompatible materials require more studies targeting their synthesis and evaluation. The aim of the present study was to evaluate the bone repair process using three osteoinductive polymers in circular bone gaps in rabbit\'s tibias. Fourty eight young adult male rabbits were divided into four experimental moments (three, seven, fourteen and thirty days). Each tibia was considered one experimental unit, in which two monocortical bone defects were made in the proximal medial region of the bone. Each experimental time was used in the following four groups: control - without biomaterial; M1 - defects protected with Poli L Lactide co Policaprolactone / Poly Ethylene Glycol; M2 - Poli L Lactide co Policaprolactone / Poly Ethylene Glycol / Tricalcium Phosphate and M3 - Poli L Lactide co Policaprolactone / Poly Ethylene Glycol / Hydroxyapatite. At the end of each period the animals were euthanized and histological sections were stained with HE, TRAP and Masson techniques. Histomorphologic and histomorphometric analysis were made and consisted in the measuring of new bone tissue formation, percentage of trabecular area, number of osteoclast and percentage of trabeculae with osteoclasts. Data were analyzed with Kruskal-Wallis and Mann-Whitney test. Results showed an incomplete absortion and no toxicity of membranes. At 14 and 30 days, control group showed bone callus in the defect, and groups M1, M2 and M3 showed bone callus in the defect and around the surface of the defect. At 30 days, the control group showed bone callus in a more mature phase in comparison to the groups with membranes. At 14 and 30 days, the bone callus area in the control group (p=0.001) was significantly smaller than the membrane groups (p=0.003). The groups with membranes exhibited signs of active remodeling at 14 and 30 days, demonstrating that the biomaterials have greater osteoinduction and osteoconduction potential. At 14 days, we found more bone formation in group M3 (nano-HA) relative to group M2 (-TCP), which may indicate that the osteoinductive / osteoconductive potentials of M3 in this bone repair phase was superior in relation to M2. The biomaterials tested in the study stimulate bone formation, but caused delayed in bone remodeling.

Neste trabalho foram preparados nanocompósitos de polímeros estirênicos com argilas organofílicas. Os polímeros estudados foram o poliestireno (PS), um copolímero tribloco de poliestireno-b-polibutadieno-b-estireno (SBS) e quatro copolímeros tribloco de poliestirenob- poli(etileno-co-butileno)-b-estireno (SEBS), sendo um deles modificado com anidrido maléico. Os nanocompósitos foram preparados por três técnicas de obtenção: mistura no fundido, solução e uma técnica híbrida que combina as duas primeiras. Os materiais obtidos foram caracterizados por difração de raios X (XRD), microscopia óptica (OM), microscopia eletrônica de transmissão (TEM), espalhamento de raios X a baixo ângulo (SAXS) e também foram realizados estudos reológicos através do ensaio de cisalhamento oscilatório de pequenas amplitudes (SAOS). O grau de dispersão de argila em algumas amostras foi avaliado por uma técnica baseada na análise de imagens obtidas por TEM. Os resultados mostraram que na maioria dos casos foram obtidos nanocompósitos intercalados, graças à presença da fase de PS em cada polímero. Amostras preparadas por solução tiveram o melhor grau de dispersão de argila, e o polímero que resultou na estrutura mais exfoliada foi o SEBS maleatado. Estudos reológicos mostraram-se muito sensíveis à formação de reticulados de partículas de argila nos nanocompósitos, que passaram a ter comportamento semelhante ao de sólidos. A combinação de técnicas de SAXS com reologia foi bastante útil para estudar a morfologia de fases ordenadas em copolímeros em bloco, permitindo identificar e distinguir estruturas lamelares, cilíndricas e esféricas em cada copolímero. Foi possível verificar que a presença de argila perturba a ordem das fases dos copolímeros e causa diferentes efeitos nas propriedades reológicas destes materiais. / In this work nanocomposites of styrenic polymers and organoclays were prepared. The polymers studied were polystyrene (PS), a polystyrene-b-polybutadiene-b-polystyrene triblock copolymer (SBS) and four polystyrene-b-poly(ethylene-co-butylene)-polystyrene triblock copolymers (SEBS), with one containing maleic anhydride. The nanocomposites were prepared using three different techniques: melt mixing, solution casting and a hybrid technique combining the former two. The materials obtained were characterized by x-ray diffraction (XRD), optical microscopy (OM), transmission electron microscopy (TEM), small angle x-ray scattering (SAXS) and by rheological studies, through small amplitude oscillatory shear tests (SAOS). The degree of clay dispersion was evaluated in some samples using a TEM image analysis technique. The results have shown that in most cases intercalated nanocomposites were obtained, due to the PS phase present in each polymer. Samples prepared by solution had the highest degree of clay dispersion, and the maleated SEBS was the polymer which originated the most exfoliated nanocomposite. The results have also shown that rheological studies are very sensitive to the formation of clay networks within the nanocomposites, which behave more solidlike. The combination of SAXS techniques and rheology was very useful to study the morphology of ordered phases in block copolymers, allowing to identify and distinguish the different structures of each copolymer, such as the lamellar, cylindrical and spherical phases. It was possible to verify that the presence of clay disturbs the phase order in the copolymers and has different effects on the rheological properties of these materials.

Esta dissertação descreve os métodos empregados na preparação por solução de filmes de copolímeros P(VDF-TrFE) nas composições molares 60/40, 70/30 e 80/20. Foram utilizadas as técnicas de deposição por centrifugação (spin coating deposition) e de espalhamento por extensor, usando acetona e metil-etil-cetona (MEK) como solventes. Filmes de boa qualidade só foram obtidos quando se acelerou o processo de evaporação do solvente, através da passagem de um fluxo de ar seco na câmara onde os filmes eram produzidos. Medidas de espectroscopia de infra-vermelho confirmaram a ausência de solvente nos filmes, já que observou-se que o pico 1715 cm-1 (carbonilha) característico do MEK não aparece nos resultados com filmes. A caracterização dos filmes fabricados foi feita através de medidas de calorimetria diferencial exploratória de varredura (DSC), difração de raios-X, espectroscopia de infra-vermelho e cromatografia líquida por exclusão de tamanho (GPC). Nos termogramas de DSC puderam ser identificadas as transições de fase ferro-paraelétrica (na temperatura de Curie, Tc) e de fusão. Os valores de Tc e da temperatura de fusão, Tf, encontrados são consistentes com os valores da literatura, com Tc aumentando com o conteúdo de VDF, ao passo que o oposto ocorre com Tf, devido ao fato que o aumento do percentual de TrFE na região cristalina aumenta a estabilidade da fase paraelétrica. Os difratogramas de Raios-X apresentaram, basicamente, um ombro largo correspondente à porção amorfa do filme, e um pico alto e estreito devido a parte cristalina do filme. No ajuste dos difratogramas através de uma função de Lorentz modificada, os resultados para as amostras de 60/40 e 70/30 foram ajustadas com três picos, o que parece indicar que pode haver duas fases cristalinas para estas amostras. Já os resultados para a amostra de 80/20 foram ajustados com apenas dois picos. O tratamento térmico das amostras, a diversas temperaturas, mostrou influenciar fortemente as propriedades dos filmes. Os seus efeitos mais importantes são o aumento da temperatura de Curie e da percentagem de cristalinidade do filme com a temperatura de tratamento / This dissertation describes the experimental methods employed in the fabrication of thin films (up to 40 micra) of the copolymer P(VDF-TrFE) for three different VDF contents, Viz. 60/40, 70/30 and 80/20. The copolymers were dissolved in either acetone or methyl-ethyl-ketone(MEK) and deposited on a solid substrate using spin coating or a sliding-knife. Good quality films could only BR obtained after dry air was flushed into the chamber where the films were fabricated. Infra-red spectrocopy measurements confirmed the abscene of solvent in the samples, as the 1715 cm-1 peak from MEK is not present in the results for the films. The film characterization was carried out using differential scanning calorimetry (DSC), X-ray diffraction, infra-red spectrocopy and gel permeation chromatography (GPC). Phase transitions could be identified in the DSC thermography which can be related to the ferro-paraelectric transition (at the Curie temperature, Tc) and to the melting of the sample. The values for Tc and the melting temperature, Tf), were consistent with those published in the literature, with Tc increasing with the contents of VDF, while the opposite is true for Tf because the increase in the TrFE contents causes the stability of the paraelectric phase to increase. The X-ray diffractograms displayed, basically, one broad halo due to the amorphous part of the film, and a eak due to its crystalline region. The diffractograms were fitted using a modified Lorentz function, where three peaks had to be assumed for the 60/40 and 70/30 samples. This appears to indicate that there may exist two crystalline phases in these samples. The results for 80/20 samples, on the other hand, were fitted with two peaks. The thermal treatment of the samples, under various temperatures, proved to influence strongly the properties of the films. Its main effects are the increase in the Curie temperature and the increase in the degree of crystallinity of the films with increasing temperature of thermal treatment

Utilizando a reação de acoplamento de Suzuki, novos polímeros e copolímeros semicondutores com elevado potencial para a fabricação de PLEDs foram sintetizados, tendo como finalidade unir em uma única camada emissiva, na forma de copolímeros ou na forma de blendas, materiais com propriedades transportadoras e injetoras de elétrons; grupos quinolina associados a materiais com elevadas propriedades de emissão de luz contendo grupos fluoreno. Esses copolímeros sintetizados, todos ainda não descritos na literatura ou em patentes, apresentaram rendimentos acima de 70% e rendimentos quânticos de fotoluminescência entre 60% e 83%, foram utilizados como camada emissiva na construção de PLEDs. Estes PLEDs foram caracterizados quanto ao seu comportamento elétrico através da obtenção de curvas de corrente em função da tensão (IxV) e dos espectros de eletroluminescência. Os resultados mostraram que a incorporação da quinolina aos copolímeros aumentou a sua estabilidade térmica, observada pela temperatura de inicio de degradação que elevou-se em até 80°C. Nos PLEDs, houve melhorias no balanceamento de cargas, dispensando até mesmo a deposição de uma camada adicional transportadora de elétrons (ETL). As tensões de operação desses dispositivos ficaram entre 2,0 e 5,2 V, com emissão entre 525 e 590nm. Esses materiais também tiveram as suas estruturas caracterizadas por ressonância magnética nuclear de hidrogênio, termogravimetria, calorimetria diferencial exploratória, espectroscopias no UV-Vis e no infravermelho, fluorimetria no UV-vis e cromatografia de permeação em gel. Filmes Langmuir e Langmuir- Blodgett dos copolímeros foram preparados e caracterizados por espectroscopia com luz polarizada de reflexão e absorção no infravermelho (PM-IRRAS) e por microscopia de força atômica (AFM). / New polymers and copolymers with a high potential for PLEDs constructions have been synthesized by Suzuki reaction and aims together in a single emissive layer in the form of copolymers or blended, materials with transporting and electron injection properties; quinoline groups linked to materials with high light emission properties as fluorene group. All these copolymers have not been described in literature or in patents, presented yields above 70%, quantum yields between 60% and 83% and were used as emissive layer in PLEDs. These PLEDs were characterized concerning their electrical behavior, by the characteristic J-V diode curves, and their electroluminescence. The results showed that the presence of quinoline increased its thermal stability at around 80° C and the PLEDs built with the synthesized copolymers do not need an extra ETL. The operating voltages of these devices were observed between 2.0 and 5.2 V with EL emission between 525 and 590nm. These new materials were also characterized by hydrogen nuclear magnetic resonance, thermogravimetry, differential scanning calorimetry, UV-Vis, Fluorescence and IR spectroscopy and gel permeation chromatography. Langmuir e Langmuir-Blodgett films were made and characterized by Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) and atomic force microscopy (AFM).

Polymer based membranes play a key role in several industrially important gas separation technologies, e.g., removing CO2 from natural gas, with enormous economic and environmental impact. In this thesis, we develop a novel hybrid membrane construct comprised entirely of inorganic nanoparticles grafted with polymer chains. For all graft architectures studied, the permeability of several small gases and condensable solvents are higher in GNP membranes than the neat polymer analogs. More interestingly, the matrix-free GNPs displayed a non-monotonic peak in gas permeability as a function of grafted chain molecular weight, M_n, at a fixed grafting density, σ. Furthermore, in contrast to neat polymer membranes, which suffer from degraded performance over time due to chain densification and “aging”, the performance of GNP membranes is preserved for months to years. We show that these enhancements are not limited to a single polymer, thus we suggest that this grafting mechanism may be an option to improve permeability in polymer membranes in general. We conjecture the grafted polymer chains must stretch to fill the interstitial voids in the NP “lattice”, as such voids would be free-energetically unfavorable due to the relatively high surface tension of the polymer melt. Since this stretching leads to an unfavorable chain conformational entropy, we expect a decrease in the polymer density, which we verify experimentally as well as through molecular dynamics simulations. When a penetrant molecule is placed in these regions of highest distortion, the chains can assume more favored, undistorted conformations. This in turn creates a driving force for further penetrant uptake. Therefore, we systematically study the structure and dynamics of matrix-free GNP materials at various chain grafting densities and a wide range of graft molecular weight. Small angle scattering experiments reveal that the core nanoparticle spacing systematically increases with increasing molecular weight but the overall morphology remains amorphous and isotropic. Whereas previous studies1 have found the brush height in matrix-free GNPs scales as the degree of polymerization 〖~N〗^0.5, we find that the brush height in our systems scales 〖~N〗^0.7, indicating the chains are indeed highly stretched. Moreover, studies of the structural evolution upon swelling with solvent show that the brush is fully wetted and the solvent distribution is homogeneous within the film. Additionally, we systematically probe the dynamics of matrix-free GNP systems over broad length and time scales using linear and non-linear mechanical rheology, and broadband dielectric spectroscopy. The linear viscoelastic response shows that while the polymeric signal (e.g. glassy and Rouse dynamics) is equivalent for a range of graft chain lengths, the terminal flow of these materials is slowed by several decades compared to the neat melts of corresponding molecular weight. The low frequency (long time) response shows that below a critical molecular weight, these systems transition from polymeric to that of a colloidal system. To understand this behavior, a scaling theory is developed to describe the polymer brush conformation, which reveals that at this transition point the grafted particles behave as a system of packed “rigid” spheres. We note that the transition point coincides with the maximum observed in the transport behavior, and that the reduced system mobility may be responsible for the reduced aging effects. On the other hand, secondary relaxations for GNPs at this transition molecular weight are found to be faster than the neat polymer of corresponding molecular weight, which is attributed to a lower effective polymer density found in these samples. Therefore, the critical question underpinning this work is: how do the structure and dynamics influence and/or result from increased free volume in matrix-free grafted nanoparticle materials? We conclude that matrix-free grafted nanoparticle constructs allow for precise control of structure-property relationships over multiple length scales, and serve as a novel materials design platform with the potential to function as high performance gas separation technologies.

Ce travail décrit la séparation de microphase à l'état solide d'un copolymère dibloc comprenant un bloc hautement biocompatible poly [2 - (méthacryloyloxy) éthyl phosphorylcholine] et un bloc pH-sensible poly [2 - (diisopropylamino) méthacrylate d'éthyle] (PMPC-b-PDPA). L'auto-assemblage d'un copolymère dibloc amphiphiles à base de polystyrène (PS) et le poly (acide acrylique) (PAA), a été étudié en suspension aqueuse, et leur décoration par du chitosane, afin de vérifier leur capacité à encapsuler et à libérer par voie transdermique la finastéride, une molécule stéroïdiens inhibiteur de la enzyme 5-alpha-réductase, qui a été recommandée pour le traitement de l'alopécie androgénétique. La morphologie des films PMPC30-b-PDPA60 a été analysée par SAXS et (S) TEM. Films du PMPC30-b-PDPA60 préparés dans une solution de l'éthanol à température ambiante présentent une morphologie cylindrique, qui subit une transition ordre-ordre sur un recuit thermique à 170 ° C: la structure lamellaire résultant coexiste avec une proportion de cylindres organisée dans une phase hexagonale compacte. En revanche, les films du copolymère préparé à partir de méthanol ne subissent pas la même transition morphologique, résultant dans des structures mal organisées, indépendante de traitement thermique. Enfin, les structures lamellaires sont obtenues directement à partir d'une solution aqueuse à pH 4, sans traitement thermique. Ces systèmes offrent une nouvelle alternative pour la fabrication de structures lamellaires constituées d'un matériau biomimétique et anti-fouling, élargissant l'éventail des possibilités dans le domaine de l'ingénierie macromoléculaire.Une autre stratégie adoptée dans ce travail a été basé sur le développement de nanoparticules bien organisé avec des propriétés de surface nature bioinspirés, formé entre polymersomes chargés négativement à base des copolymères à blocs de polystyrène (PS) et le poly (acide acrylique) (PAA) décorés avec du chitosane, un polysaccharide de charge opposée. Le rôle de l'adsorption du chitosane avec deux poids moléculaires distincts (chitosane oligosaccharides et du chitosane avec un faible poids moléculaire) sur la surface des nanoparticules PS139-b-PAA17 et des nanoparticules PS404-b-PAA63 ont été démontrés par diffusion dynamique de la lumière, potentiel zêta et caractérisation morphologiques. En présence du chitosane, le potentiel zêta de polymersomes devient positif. Ce résultat a été interprété en termes d'interactions électrostatiques, qui induisent une adsorption du chitosane sur la surface des polymersomes. Ce résultat a été confirmé par une observation comparative par microscopie entre des polymersomes et des polymersomes décorées. Polymersomes avec un diamètre <200 nm et une distribution granulométrique relativement étroite ont été obtenus pour les deux systèmes. L'effet de la décoration des nanoparticules par du chitosane sur la perméation cutanée in vitro du finastéride, incorporé dans la paroi hydrophobe de polymersomes, a également été évaluée. La pénétration cutanée du finastéride a été estimée par les paramètres de perméabilité tels que le flux, temps de latence et du coefficient de perméabilité de la finastéride. Une amélioration de la perméation du finastéride à partir des nanoparticules a été observée, en particulier à partir de nanoparticules décorées avec du chitosane. Le polymersome PS404-b-PAA63 décorées avec du chitosane semble être le système le plus approprié car il favorisé une meilleure rétention du médicament dans la peau et les faibles valeurs de flux de perméation, suggérant que le système fournit un véhicule de remplacement pour l'administration transdermique de finastéride. / This work describes the microphase separation in bulk of an diblock copolymer comprising a highly biocompatible poly[2-(methacryloyloxy)ethyl phosphorylcholine] block and a pH-sensitive poly[2-(diisopropylamino) ethyl methacrylate] block (PMPC-b-PDPA). The self-assembly of an amphiphilic diblock copolymer based on polystyrene (PS) and poly(acrylic acid) (PAA) was studied in terms of their decoration with the chitosan, verifying their ability to incorporate and transdermally release the drug finasteride, a steroidal molecule 5-alpha-reductase inhibitor that has been recommended for the treatment of androgenetic alopecia. The morphology of PMPC30-b-PDPA60 films was analyzed using SAXS and (S)TEM. PMPC30-b-PDPA60 films cast from ethanol solution at room temperature exhibit a thermodynamically quasi-stable cylindrical morphology, which undergoes an order-order transition upon thermal annealing at 170 oC: the resulting lamellar structure coexists with a minor proportion of cylinders organized into a hexagonal compact phase. In contrast, copolymer films cast from methanol do not undergo the same morphological transition. Instead, short-range liquid-like structures are obtained regardless of the annealing processes. Finally, direct self-assembly to form a lamellar morphology at room temperature can be achieved by solvent-casting from aqueous solution at pH 4. These systems offer a new alternative for the fabrication of lamellar structures in which one layer is biomimetic and non-fouling, expanding the range of possibilities in the macromolecular engineering field. Another strategy adopted in this work was based on the development of well-organized nanoparticles with nature-bioinspired surface properties, formed between negatively charged polymersomes based on polystyrene (PS) and poly(acrylic acid) (PAA) block copolymers decorated with chitosan, an oppositely charged polysaccharide. The role of chitosan with two distinct molecular weights (chitosan oligosaccharide and low molecular weight chitosan) adsorption on the surface of oppositely charged PS139-b-PAA17 and PS404-b-PAA63 nanoparticles were demonstrated by dynamic light scattering measurements, zeta potential and morphological characterization. In the presence of chitosan, the zeta potential of polymersomes becomes positive. This result was interpreted in terms of electrostatic interactions, which induce a flat adsorption of the chitosan on the surface of the polymersomes. This result was further confirmed by a comparative observation by microscopy of bare and chitosan-decorated polymersomes. Polymersomes with a diameter < 200 nm and a relatively narrow size distribution were obtained for both systems. The effect of chitosan decoration of self-assembled nanoparticles on skin penetration in vitro of finasteride was also evaluated, once incorporated in the wall hydrophobic of polymersomes. The skin permeation through pig ear skin of finasteride was estimated by the permeability parameters such as flux, lag time and permeability coefficient of finasteride. An improved permeation of finasteride from the nanoparticle system was observed, especially from nanoparticles decorated with chitosan. The PS404-b-PAA63 polymersome decorated with chitosan seems to be the most appropriate system since it provided higher drug retention in skin and low permeation flux values, suggesting that the PS-b-PAA/chitosan system provides an alternative for transdermal drug delivery system of finasteride.