As fraturas em equinos são responsáveis por grande prejuízo financeiro devido às dificuldades encontradas para instituir seu tratamento nessa espécie, principalmente em animais adultos. Entre as dificuldades técnicas no tratamento de fraturas em equinos estão a alta resistência óssea, que acarreta fraturas com grande transmissão de energia, e a escassez de materiais e técnicas de osteossíntese específicos para a espécie, gerando mau prognóstico em muitos casos. Estas fraturas, quando cominutivas acarretam em falhas ósseas, criando um espaço entre os fragmentos de maior tamanho e ainda extensa lesão de tecidos adjacentes, o que dificulta e prolonga o tempo de consolidação óssea. Atualmente a terapia com células tronco vem sendo bastante estudada em ortopedia, contudo o ambiente onde essas células são depositadas determina o caminho para onde elas vão se diferenciar. Para a utilização de células tronco em ortopedia, estas devem sem implantadas junto a um suporte tridimensional, por exemplo os biopolímeros, que além de fornecer um meio para a multiplicação e diferenciação dessas células, também deve apresentar características biomecânicas semelhantes ao tecido a ser reparado, que no caso da ortopedia é o tecido ósseo. O objetivo desse estudo foi avaliar as propriedades biomecânicas de dois biopolímeros a poliuretana de mamona com carbonato de cálcio e uma formulação de quitosana com fosfato de cálcio. Foram preparadas duas formulações diferentes de cada biopolímero, em corpos de prova cilíndricos de 12 mm de comprimento e 6 mm de diâmetro, sendo: poliuretana de mamona porosa e compacta, e quitosana com secagem a 38 e 60 graus Celsius. Essas formulações foram submetidas a ensaios compressivos nos momentos 3, 24, 48 e 72 horas após o preparo e avaliadas quanto sua resistência à compressão, deformação relativa e módulo de elasticidade. A poliuretana de mamona compacta apresentou o maior valor de resistência à compressão (45,805 N/mm2) após 48 horas. A fórmula de quitosana com secagem a 38oC apresentou a menor deformação relativa (3,952 %) após 72 horas de preparo e o maior valor de módulo de elasticidade encontrado foi na poliuretana de mamona compacta após 72 horas (1354,284 N/mm2). Sendo assim a poliuretana de mamona compacta apresenta maior resistência à compressão do que o osso esponjoso de terceiro metacarpiano equino e semelhante aos substitutos ósseos comerciais mais resistentes. A fórmula de quitosana 38oC apresentou valores similares aos observados no osso esponjoso equino. Podemos concluir com esses dados que a poliuretana de mamona compacta e a fórmula de quitosana 38oC apresentam características biomecânicas desejáveis nos materiais para enxerto ósseo. / Equine fractures are responsible for great economic losses due to difficulties in establishing their treatment, mainly regarding adult animals. Among technical difficulties faced in the equine fractures treatment, there are high bone strenght, which results in high energy fractures and the lack of materials and specific osteosynthesis techniques for the specimen, resulting bad prognostic in many cases. When cominutives, these fractures result in bone gaps, creating spaces between bigger fragments and still extensive surrounding tissue damages, which difficults and extends time for bone consolidation. Nowadays, therapy with steam cells is focused in orthopedy, but environment where these cells are established determines the path they will take. For the use of steam cells in orthopedy, they must be implanted together with a tridimensional support such as biopolymers which, besides offering conditions for replication and differentiation of these cells, they must present biomechanic characteristics similar to the tissue to be healed, which is the bone. The target of this study was to evaluate biomechanic properties of two biopolymers, a castor oil polyurethane with calcium carbonate and a formulation of chitosan with calcium phosphate. Two different formulations of each biopolymer were prepared, in cilindric parts of 12mm lenght and 6mm diameter: porous and compact castor oil polyurethane, and chitosan drying at 38oC and 60oC. These formulations were submitted to compressed tests at 3, 24 and 72 hours after preparation and evaluated for compressive strenght, relative deformation and modulus of elasticity. The compact castor oil polyurethane presented greater compressive value (45,805 N/mm2) after 48 hours. Chitosan formulation drying at 38oC presented lower relative deformation (3,952%) 72 hours after prepared, and the highest value for modulus of elasticity found was compact castor oil polyurethane after 72 hours (1354,284 N/mm2). Thus, compact castor oil polyurethane presents higher compressive strenght than trabecular bone of the third equine metacarpal and similar to strenghter comercial bone grafts. The formulation chitosan 38oC presented similar values to those observed in equine trabecular bone. With these data, we can conclude that the compact castor oil polyurethane and the formulation of chitosan 38oC present desirable biomechanic characteristics in materials for bone grafts.

<p>There is an increased discharge of produced water in the USA, which is causing decrease in the amount of usable water and is being rendered useless by refinery and extraction operations. Produced water that is obtained from these activities is usually not feasible to be used in any form. So, it becomes necessary to get the water to a quality standard, as per the US EPA, which will make this water suitable for both commercial as well as household purposes.</p><p> </p><p>There have been a number of studies on Au, Ag and Carbon Nanotubes solar enabled steam generation with potential applications in water purification, distillation and sterilization of medical equipment. The key challenge with these nanoparticles is cost of production, hence limiting its wide application for clean water production. This work, for the first time, reports on activated carbon enabled steam generation hence addressing the cost limitations of metallic nanoparticles. Activated carbon has high solar absorptivity at various wavelengths of visible light.</p><p> </p>This work uses Activated Carbon coated Polyurethane foam to simultaneously adsorb oil from the produced water and also yield surface vapors under application of solar light to get a clean distillate which can be used in various ways be it commercial or household. The given fabricated system will be an inexpensive and simple method to get clean water. The temporal evolution of the distillate has been measured as well as the temperature characteristics. Experiments were carried out using activated carbon and CNT nanofluids and polyurethane membrane with immobilized activated carbon and CNT. A simulated solar light of 1 KW ~1 Sun was used. The rate of evaporation, temporal and spatial evolution of bulk temperature in the water were monitored automatically and recorded for further data reductions. Parametric studies of the effect of nanoparticle concentration, water quality and salinity were performed. Experimental evidence showed that activated carbon has potential. Previous work reported for the first time that optimal activated carbon concentration for maximum steam generation is 60 % vol. There was a 160 % increase in steam production rate at 60 % concentration of activated carbon when compared with D.I. water.Different atmospheric conditions were varied and the concentration of the sun to see the effects on the production of water. The recovery capacity of the foam was also tested so as to determine the waste oil that can be obtained from the foam and if the foam can be reused without being disposed of. More than 95% oil can be recovered The quality analysis has been performed and is an integral focus of the work as the comparison with the USA EPA (Environmental Protection Agency) will make it more robust and real world ready. The inclusion of Polyurethane foam, which is a major accumulating waste in the environment because of its use in packaging industry, and solar light as the energy source, to drive the distillation process, makes this a very clean and green process to treat produced water.

This dissertation focuses on the versatility and integrity of a novel, ultrasoft polycarbonate polyurethane (PCPU) by the introduction of nanoparticles and lithium salts. Additionally, the research takes into account the use of electrospinning as a technique to create PCPU and polyimide (PI) fibers. These polymers are of interest as they offer a wide range of properties and uses within the medical and industrial fields. An industrial batch of an ultrasoft thermoplastic polyurethane (TPU) was synthesized using a two-step process. The first was to create an end capped pre-polymer from methylene bis (4-cyclohexylisocyanate), and a polycarbonate polyol made up of 1,6- hexanediol and 3-methyl-1,5-pentanediol. The second step was done by reacting the pre-polymer with an excess of the polycarbonate polyol with a chain extender, 1,4-butanediol. Biocompatibility testing such as USP Class VI, MEM Elution Cytotoxicity and Hemolysis toxicology reported that PCPU showed no toxicity. This novel type of polyurethane material targets growing markets of biocompatible polymers and has been used for peristaltic pump tubing, but also can be utilized as balloon catheters, enteral feeding tubes and medical equipment gaskets and seals. This material is ideal for replacing materials such as soft plastisols containing diethylhexyl phthalate for use in biomedical and industrial applications. After extensive characterization of this polymer system another dimension was added to this research. The addition of nanoparticles and nanofillers to polyurethane can express enhanced mechanical, thermal and adhesion properties. The incorporation of nanoparticles such as nanosilica, nanosilver and carbon black into polyurethane materials showed improved tensile strength, thermal performance and adhesion properties of the PCPU. Samples were characterized using contact angle measurements, Fourier transform spectroscopy (FTIR), differential scanning calorimetry (DSC), parallel plate rheology and tensile testing. The second chapter entails the fabrication and characterization of PCPU nanofibers and nanomembranes through a process known as electrospinning. The resulting PCPU nanomembranes showed a crystalline peak from the WAXS profile which is due to electrospun and solution strain induced crystallinity. The PCPU nanocomposite nanomembranes displayed increased thermal stability and an increase in tensile performance at higher weight percent. The nanomembranes were investigated using contact angle measurements, thermogravimetric analysis (TGA), DSC, WAXS, SAXS and tensile testing. The final chapter focuses on investigating the rheological properties of PCPU/lithium electrolytes as well as transforming an unprocessable polyimide powder into a nanomembrane. The PCPU/ lithium composite electrolyte showed an increase in the activation energy and conductivity, while the PI/lithium showed increased conductivity over time. Dynamic mechanical analysis and four-point probe was used to investigate the samples.

This thesis covers sampling and analytical procedures for isocyanates (R-NCO) and amines (R-NH2), two kinds of chemicals frequently used in association with the polymeric material polyurethane (PUR). Exposure to isocyanates may result in respiratory disorders and dermal sensitisation, and they are one of the main causes of occupational asthma. Several of the aromatic diamines associated with PUR production are classified as suspected carcinogens. Hence, the presence of these chemicals in different exposure situations must be monitored. In the context of determining isocyanates in air, the methodologies included derivatisation with the reagent di-n-butylamine (DBA) upon collection and subsequent determination using liquid chromatography (LC) and mass spectrometric detection (MS). A user-friendly solvent-free sampler for collection of airborne isocyanates was developed as an alternative to a more cumbersome impinger-filter sampling technique. The combination of the DBA reagent together with MS detection techniques revealed several new exposure situations for isocyanates, such as isocyanic acid during thermal degradation of PUR and urea-based resins. Further, a method for characterising isocyanates in technical products used in the production of PUR was developed. This enabled determination of isocyanates in air for which pure analytical standards are missing. Tandem MS (MS/MS) determination of isocyanates in air below 10-6 of the threshold limit values was achieved. As for the determination of amines, the analytical methods included derivatisation into pentafluoropropionic amide or ethyl carbamate ester derivatives and subsequent MS analysis. Several amines in biological fluids, as markers of exposure for either the amines themselves or the corresponding isocyanates, were determined by LC-MS/MS at amol level. In aqueous extraction solutions of flexible PUR foam products, toluene diamine and related compounds were found. In conclusion, this thesis demonstrates the usefulness of well characterised analytical procedures and techniques for determination of hazardous compounds. Without reliable and robust methodologies there is a risk that exposure levels will be underestimated or, even worse, that relevant compounds will be completely missed.

A degradable/polar/hydrophobic/ionic (D-PHI) polyurethane with properties intended to promote tissue regeneration in a small diameter peripheral artery vascular graft was evaluated for cell biocompatibility and growth. Films were cast in polypropylene 96 well plates for monocyte/endothelial cell (EC) co-culture in vitro studies and porous scaffold discs were implanted in an in vivo subcutaneous mouse model. After 7 days in culture the co-culture demonstrated cell adhesion and growth, low esterase activity (a measure of degradative potential and cell activation), no detectable release of pro-inflammatory cytokine (tumour necrosis factor -α) but measurable anti-inflammatory interleukin (IL)-10. The EC and the co-culture expressed the EC biomarker CD31, whereas the monocyte monoculture did not. Cytokine array analysis of the in vivo characterization of D-PH supported an anti-inflammatory phenotype of cells at the site of the implant. Levels of IL-6 significantly decreased over time while IL-10 was significantly higher at 6 weeks post implant. TNF-α levels did not change significantly from 24 hours onwards, however the trend was towards lesser amounts following the initial time point. Histological analysis of the explanted scaffolds showed excellent tissue ingrowth and vascularization. A live/dead stain showed that the cells infiltrating the scaffolds were viable. Both the in vitro and in vivo results of this thesis indicate that D-PHI is a good candidate material for tissue engineering a peripheral artery vascular graft.

A degradable/polar/hydrophobic/ionic (D-PHI) polyurethane with properties intended to promote tissue regeneration in a small diameter peripheral artery vascular graft was evaluated for cell biocompatibility and growth. Films were cast in polypropylene 96 well plates for monocyte/endothelial cell (EC) co-culture in vitro studies and porous scaffold discs were implanted in an in vivo subcutaneous mouse model. After 7 days in culture the co-culture demonstrated cell adhesion and growth, low esterase activity (a measure of degradative potential and cell activation), no detectable release of pro-inflammatory cytokine (tumour necrosis factor -α) but measurable anti-inflammatory interleukin (IL)-10. The EC and the co-culture expressed the EC biomarker CD31, whereas the monocyte monoculture did not. Cytokine array analysis of the in vivo characterization of D-PH supported an anti-inflammatory phenotype of cells at the site of the implant. Levels of IL-6 significantly decreased over time while IL-10 was significantly higher at 6 weeks post implant. TNF-α levels did not change significantly from 24 hours onwards, however the trend was towards lesser amounts following the initial time point. Histological analysis of the explanted scaffolds showed excellent tissue ingrowth and vascularization. A live/dead stain showed that the cells infiltrating the scaffolds were viable. Both the in vitro and in vivo results of this thesis indicate that D-PHI is a good candidate material for tissue engineering a peripheral artery vascular graft.

Many heterocyclic compounds containing nitrogen, oxygen and sulfur show wide range of physiological activities and their synthesis has always been attracted the interest of chemists. The aim of this research is to develop new synthetic methodologies leading to the synthesis of new derivatives of isocoumarines, indoles, isoquinolines, benzodiazepinones and quinazolines, which have been found to show important biological activities. Starting from homophthalic acid and bishomophthalic acid the corresponding acyl azides were proposed to be synthesized, which then would be used for the synthesis of various heterocycles. The proposed diazide from homophthalic was not formed due to the tendency of the ortho-positioned acid to undergo cyclization. Instead, new unusual benzochromen and isocoumarin derivatives have been synthesized in a single step, for which reasonable mechanisms have been proposed. The half ester produced from homophthalic acid was an important key compound for the synthesis of new highly substituted indole derivatives, which are expected to be biologically active. The diisocyanate derived from was synthesized directly from ortho-bromo xylene was treated with alcohols and hydrazine to produce seven membered rings. Instead of the intramolecular cyclization reaction, they underwent polymerization to form new polymers. Furthermore, new synthetic method for the synthesis of pyrazoles has been developed.

Zeolites are nanoporous crystalline aluminosilicates that are tasteless, odorless and nontoxic to humans. They can be tailored into antibacterial agents that are more cost effective than other conventional alternatives. Considering the increasing demand for enduring antibacterial agents, the potential uses of antibacterial zeolites are numerous in medical applications and for everyday household products. To produce antibacterial zeolites, the extra framework cations in the zeolite structures can be exchanged with silver ion (Ag+), the most commonly used antibacterial heavy metal ion due to its high stability, strong activity and broad spectrum. Utilization of antibacterial zeolite powders can be diversified when they are used as fillers in a polymer matrix. Polyurethanes (PU) are a class of polymers which can be prepared in wide range of physical structures with excellent mechanical properties. Ag+ loaded zeolites used as fillers in the PU matrix would contribute to the diversity and efficiency of the PU utilization in many applications including biomedical uses and consumer products. In this study, three types of zeolites, namely / zeolite Beta, X and A with different pores sizes and SiO2/Al2O3 ratios were synthesized hydrothermally and treated with Ag+ containing solution for the exchange of cations. Composites were prepared by incorporation of sieved Ag+ exchanged zeolite particles into biomedical grade PU prepolymers which were prepared either in film or as sponge forms. Films were prepared by molding and foams were prepared in the presence of water as the blowing agent. Liquid media antibacterial tests showed that all of the Ag+-zeolite powders were effective against E. coli at a concentration of 500 ppm zeolite in deionized water. To assess the antibacterial effect of composites against E. coli, disc diffusion tests were carried out. Bacterial growth inhibition zones formed around the composite samples were the evidence of the antibacterial activity in the vicinity of the surface. All three kinds of zeolites successfully introduced the desired antibacterial property to the biomedical grade PU both in elastomeric film and in the foam form. Mechanical characterization of the composites yield higher ultimate tensile strength, modulus of elasticity and elongation at break values compared to control PU. No significant change in thermal properties of the composites was observed. Hence mechanical and thermal characterization of the composites showed that zeolites serve for the reinforcement of the mechanical properties of the polymer and did not cause any deterioration in thermal properties.

Thrombus formation and blood coagulation is a major problem associated with blood contacting products such as catheters, vascular grafts and artificial hearts. An intense research is being conducted towards the synthesis of new hemocompatible materials and mdifications of surfaces with biological molecules. In this study, polyurethane (PU) films were synthesized in medical purity from diisocyanate and polyol without using any other ingredients and the chemical, thermal and mechanical properties were characterized by solid state NMR, FTIR, GPC, mechanical tests, DMA and TGA. The surfaces of PU films were modified by covalent immobilization of different molecular weight heparins / low molecular weight heparin (LMWH) and unfractionated heparin (UFH) and these surfaces were examined by ESCA, ATR-FTIR, AFM and contact angle goniometer. Cell adhesion studies were conducted with whole human blood and examined by SEM. The effects of different types of heparins on blood protein adsorption and on platelet adhesion were analyzed by electrophresis and SEM, respectively. The surfaces of the UFH immobilized polyurethane films (PU-UFH) resulted in lesser red blood cell adhesion in comparison to LMWH immobilized polyurethane film surfaces (PU-LMWH). When the PU films were treated with blood plasma, the surfaces modified with two different heparin types showed a clearly different protein adsorption behavior especially in the early stage of blood plasma interaction. PU-LMWH samples showed about three times less protein adsorption compared to PU-UFH samples. The morphologies of platelets adhered on material surfaces demonstrated differences / such as PU-UFH had clusters with some pseudopodia extensions, while PU-LMWH had round shaped platelets with little clustering. PU surfaces modified by immobilization of LMWH and UFH, demonstrated promising results for the improvement of non-thrombogenic devices and surfaces.

This study was aimed to synthesize low molecular weight hydroxyl terminated polyurethane acrylate polymers that can be used in biomedical applications. Acrylate end capping via inter-esterification reaction was successfully achieved with the methacryloyl chloride addition to the hydroxyl ends of the polyurethane at low temperatures. Isocyanate terminated polyurethane acrylates were also synthesized for the sake of comparison. TDI, HDI and MDI were used as diisocyanates for urethane synthesis and they were end capped with MMA and HEMA. Nature of the monomers used had an effect on thermal, morphological, and rheological properties that were interpreted in terms of the level of hydrogen bonding and degree of phase separation. Synthesized polymers were characterized by NMR, FTIR-ATR, DSC, TGA, GPC, Mass Spectroscopy, SEM and rheometry. In the literature, polyurethane acrylate polymers have been synthesized from the isocyanate terminated polyurethanes in which the urethane chains were ended with isocyanate groups. However, the toxicity of the isocyanate groups limited their biomedical applications especially in prosthetic dentistry as a soft lining material. Therefore, it is inevitable to explore the cytotoxicity of polyurethane acrylate polymers. For this purpose, silver nanoparticles that have an average particle size of 40 nm, were incorporated to the synthesized polymers. This addition, which intends to improve the degree of cytotoxicity, was successful to a certain extent.