RESUMO Este trabalho tem como objetivo a preparação de mantas compostas por fibras do polímero biodegradável poli(3-hidroxibutirato) -(PHB) por meio da técnica de eletrofiação. Obtiveram-se mantas sob diferentes condições, variando-se o fluxo, a temperatura da solução, a tensão aplicada e a adição de um agente surfactante. O material obtido foi analisado por microscopia eletrônica de varredura (MEV), calorimetria exploratória diferencial (DSC), termogravimetria (TG), difratometria de raios-X (DRX) e viabilidade celular. A caracterização por MEV mostrou que os melhores resultados, apresentando as fibras com diâmetros constantes de 0,77 µm e sem a formação de grãos, foram atingidos nas seguintes condições: concentração da solução de 10% (m/v) em CF/DMF (9/1), fluxo da solução de 5,8 ml/h, tensão de 17 kV e adição de surfactante (dodecilsulfato de sódio, SDS). Os resultados mostraram que as variações de vazão, tensão e a adição de surfactante não influenciam muito o diâmetro médio das fibras, enquanto o aumento da temperatura diminui este parâmetro. No entanto, a adição de um agente surfactante deixa a manta mais densa e com poros interconectados, além de permitir a proliferação celular, sendo então indicada para produção de mantas para uso como arcabouço.

ABSTRACT This work aims the preparing of mats composed of poly (3-hydroxybutyrate) -(PHB) biodegradable polymeric fibers, using the electrospinning technique. Mats were obtained under different conditions: changing the flow and temperature of the solution, tension and the addition of a surfactant to the solution. The obtained material was analyzed by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TG), X ray diffractometry (XRD) and cell viability. The characterization by SEM showed that the best results, presenting fibers with constant diameters of 0.77 μm and without beads formation, were reached under the following conditions: concentration of 10% (m / v) solution in CF / DMF (9/1), solution flow of 5.8 ml/h, 17 kV and addition of surfactant (sodium dodecylsulfate, SDS). The results showed that the variation of the flow, tension and surfactant did not influence the average diameter of the fibers, but the increase of the temperature decreases this parameter. Moreover, the addition of a surfactant increases the density of the blankets and interconnect the pores, allowing cellular proliferation, and, thus. it is indicated for use as scaffolds.

Resumo Os dispositivos de fixação óssea, metálicos convencionais, usados em cirurgia crâniomaxilofacial têm apresentado alguns problemas, tais como, corrosão, inflamação e infecção, além de neoformação de estrutura óssea mecanicamente inferior devido à atrofia gerada pela diferença de módulo elástico entre metal e osso, razões que têm levado ao aumento do interesse por dispositivos poliméricos bioarreabsorvíveis. Os polímeros biorreabsorvíveis mais utilizados nesta aplicação pertencem à família dos poli (α-hidroxi ácidos), que têm como característica degradarem por hidrólise de suas ligações ésteres, tal como copolímero poli (L-ácido láctico-co-D, L ácido láctico), PLDLA. Neste trabalho foram investigados alguns efeitos da adição de poli (caprolactona triol), PCL-T sobre PLDLA. Foram preparados pinos por fusão de blendas nas seguintes composições 100/0, 90/10, 70/30 and 50/50 (m/m), PLDLA/PCL-T. Os pinos foram caracterizados por diferentes técnicas (DSC, MEV e ensaio mecânico). A degradação in vitro dos pinos foi investigada, sendo observado que a adição de PCL-T no PLDLA modificou suas propriedades mecânicas e morfológicas. Tais mudanças podem apresentar potencial para outras aplicações do material, onde a questão da flexibilidade se faça necessária.

Abstract The bone fixation devices, conventional metallic cranium used in surgery have presented some problems, such as corrosion, inflammation and infection, and a lower mechanically newly formed bone structure due to the atrophy caused by the difference in stiffness between metal and bone. These reasons have led to increased interest in bioreabsorbable polymeric devices. The most bioresorbable polymers used in this application belong to the family of poly (α-hydroxy acids), which are characterized degrade by hydrolysis of its ester linkages, such as copolymer poly (L-lactic acid-co-D, L lactic acid) (PLDLA). In this work was investigated some effects of the addition poly (caprolactone triol), PCL-T in the PLDLA. Pins were prepared by melting in the 100/0, 90/10, 70/30 and 50/50 (w/w) compositions, PLDLA/PCL-T. The pins were characterized by different methods (DSC, SEM and mechanical test). The in vitro pins degradation was investigated. It was observed that the addition of PCL-T of PLDLA modifies the mechanical properties, morphological, we conclude that PLDLA/PCL-T can be a potential material for various applications, where the question of flexibility to make necessary.

This study aims the synthesis of copolymers of poly (l-lactic acid) and polycaprolactone by ring opening polymerization. The reactions between l-lactide (LLA) and ε-caprolactone (CL) monomers, in 100/0, 95/5, 90/10 and 80/20 LLA/CL mass ratios, were conducted in refluxing toluene, using Stannous octoate as iniciator, methanol as co-iniciator and inert atmosphere (N2). The reaction medium was maintained under stirring at 120 °C for 24 hours. The samples were characterized by carbon-13 and proton nuclear magnetic resonance (C13-NMR and H1-NMR), and gel permeation chromatography (GPC). Monomers were characterized by thermogravimetry (TG). Copolymers were formed only in samples containing 20 wt% ε-caprolactone. NMR spectra of the other samples showed no evidence of CL units. This fact may be associated with the low-temperature volatilization of monomers. The GPC analysis showed that the increase of CL concentration decrease the molecular weight of copolymers.

The application of polymer-based bioresorbable temporary devices in the medical field grows continuously, and professionals from several areas act to solve problems related to body functions lost due to diseases, accidents or natural wear. Here we study the influence from poly(caprolactonetriol) (PCL-T) on the degeneration process in the copolymer poly(L-co-DL-lactic acid) (PLDLA) membrane, by producing PLDLA/PCL-T blends with 90/10, 70/30 and 50/50 relative concentrations. The data for in vitro degradation showed that PCL-T decreases the rate of PLDLA. This was obtained with the following techniques: Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Gel Permeation Chromatography (GPC) and Scanning Electron Microscopy (SEM). Therefore, it is possible to vary the membrane degradation rate by changing the blend composition, which is a tool to tailor a biomaterial.

Poly (L-co-D,L lactic acid) (PLDLA) is an important biomaterial because of its biocompatibility properties that promote cellular regeneration and growth. The aim of this study was to evaluate the polymer-tissue interaction of PLDLA implants in the dorsal subcutaneous tissue of male Wistar rats at various intervals (2, 7, 15, 30, 60 and 90 days) after implantation. Physical properties such as the glass transition point (Tg), degradation behavior and other mechanical properties were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), scanning electron microscopy (SEM) and tension tests. Analysis of the degradation of PLDLA membranes in vitro showed that the polymer became crystalline as a function of the degradation time. Mechanical tension tests showed that the polymer behaved like a ductile material: when subjected to constant tension it initially suffered deformation, then elongation and finally ruptured. TGA/MEV provided evidence of PLDLA membrane degradation. For histological analysis, samples from each group were processed in xylol/paraffin, except for the 60 - and 90 - day samples. Each of the latter samples was divided in two: one half was treated with xylol/paraffin and the other with historesin. Light microscopy showed the adhesion of cells to the biomaterial, the formation of a conjunctive capsule around the implant, the presence of epithelioid cells, the formation of foreign body giant cells and angiogenesis. During degradation, the polymer showed a 'lace' - like appearance when processed in xylol/paraffin compared to the formation of "centripetal cracks in the form of glove fingers" when embedded in historesin.

Aiming the development of high-performance biodegradable polymer materials, the properties and the processing behavior of poly(3-hydroxybutyrate), P(3HB), and their blends with poly(epsilon-caprolactone), PCL, have been investigated. The P(3HB) sample, obtained from sugarcane, had a molecular weight of 3.0 x 10(5) g.mol¹, a crystallinity degree of 60%, a glass transition temperature (Tg), at - 0.8 °C, and a melting temperature at 171 °C. The molecular weight of PCL was 0.8 x 10(5) g.mol-1. Specimens of 70/30 wt. (%) P(3HB)/PCL blends obtained by injection molding showed tensile strength of 21.9 (± 0.4) MPa, modulus of 2.2 (± 0.3) GPa, and a relatively high elongation at break, 87 (± 20)%. DSC analyses of this blend showed two Tg´s, at - 10.6 °C for the P(3HB) matrix, and at - 62.9 °C for the PCL domains. The significant decrease on the Tg of P(3HB) evidences a partial miscibility of PCL in P(3HB). According to the Fox equation, the new Tg corresponds to a 92/8 wt. (%) P(3HB)/PCL composition.