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Los sistemas poliméricos multifásicos han recibido una considerable atención en las últimas décadas. En particular, los copolímeros bloque presentan un marcado interés no sólo desde el punto de vista académico sino también desde el tecnológico, porque permiten obtener nuevos materiales con propiedades específicas cuya principal característica es la presencia de dos o más fases en estado sólido en la escala de los nanómetros. En la mayoría de los casos, los copolímeros bloque están constituidos por segmentos termodinámicamente incompatibles que se encuentran unidos químicamente en una sola molécula. Algunos ejemplos son: combinación de bloques hidrofóbicos con hidrofílicos, para aplicaciones como espesan-tes, absorbentes o compatibilizantes para la industria cosmé-tica. Por otra parte los copolímeros bloque presentan proce-sos de separación en microfases o formación de estructuras auto-ensambladas que los convierte en excelentes candidatos para aplicaciones en nanotecnología y electrónica. En esta Tesis se sintetizaron y caracterizaron copolímeros bloque en base siloxano, con estructura definida, empleando polimeri-zación aniónica en alto vacío. En particular se sintetizaron copolímeros de estireno-dimetilsiloxano, butadieno-dimetilsi-loxano, metil-metacrilato-dimetilsiloxano y estireno--caprolac-tona con estructuras y composiciones definidas con el objeti-vo de encontrar condiciones de reacción adecuadas para la síntesis de estos materiales. Los copolímeros obtenidos fueron caracterizados química y térmicamente empleando numerosas técnicas analíticas tales como Cromatografía por Exclusión de Tamaños (SEC); Resonancia Magnética Nuclear de hidrógeno (1H-NMR), Espectroscopia Infrarroja con Transformada de Fourier (FTIR), Difracción de Rayos X de bajo ángulo (SAXS), Calorimetría Diferencial de Barrido (DSC), Análisis Termogra-vimétrico (TGA) y Microscopía Óptica de luz Polarizada (POM) entre otras. Todos los copolímeros mostraron tener un control adecuado de las masas molares, presentando bajos índices de polidispersión para un amplio rango de masas molares y compo-siciones, además los resultados permitieron corroborar la formación de nanoestrucuras tanto en masa como en solución. Los resultados informados en esta Tesis constituyen un apor-te de interés respecto a la síntesis y caracterización de copo-límeros de estructura molecular definida basados en siloxano y ε-caprolactona. En tal sentido, los resultados obtenidos per-miten ampliar y profundizar la información existente en cuanto a la morfología en masa y en solución de copolímeros bloque basados en siloxano, y a las características térmicas de copo-límeros con un bloque semicristalino de poli(ε-caprolactona). / In the last decades, multiphase polymer systems have received widespread attention. In particular, block copolymers are of both academic and technological interest because they can generate new materials with enhanced or specific properties. These materials are usually characterized by the presence of two or more polymeric phases in the solid state at the nanometer scale. In all cases, block copolymers are made of thermodynamically incompatible segments chemically bonded. Some examples are: combination of hydrophobic and hydrophilic blocks for applications such as thickeners, absor-bents or compatibilizers for cosmetics industry. Moreover, block copolymers exhibit microphase separation processes given self-assembled structures which are excellent candida-tes for nanotechnology and electronic applications. This Doc-toral Thesis reports the results for well-defined synthesis and characterization of block copolymers based on siloxane using high vacuum anionic polymerization techniques. Particularly, several synthesis reactions were performed during the course of the experimental research and styrene-dimethylsiloxane, butadiene-dimethylsiloxane, methylmetacrylate-dimethylsilo-xane, and styrene--caprolactone copolymers were obtained with well-defined molar mass and narrow polydispersity. Obtained block copolymers were chemically and thermally characterized by Size Exclusion Chromatography (SEC), Nuclear Magnetic Resonance (1H-NMR), Fourier Transform Infrared Spectroscopy (FTIR), Small Angle X-ray Scattering (SAXS), Differential Scanning Calorimetry (DSC), and Polarized Optical Microscopy (POM), among others. All the copolymers showed a well-defined molar mass and narrow polydispersity for a wide range of molar masses and compositions, which allows the study of nanostructures obtained both in mass and in solution. Reported results are an interesting contribution regarding the synthesis and characterization of well-defined copolymers based on siloxane and ε-caprolactone. In these sense, the obtained information extend and to deepen the existing information on both mass and solution morphology of siloxane based block copolymers and thermal characteristics of semicrystalline poly(ε-caprolactona).

O problema do resíduo plástico vem se tornando crucial nos últimos anos no que concerne aos problemas ambientais. Neste cenário, a preparação de compósitos baseados em polímeros e fibra naturais, tais como as da casca de coco, levaria à redução do custo do produto final e a consequente diminuição da quantidade de resíduo do agronegócio descartado no meio ambiente. No Brasil, a produção anual de coco é por volta de 1,5 bilhões de frutos em uma área cultivada de 2,7 milhões de hectares. Porém, a fibra da casca do coco tem sido pouco utilizada para aplicações industriais, representando um componente importante no montante de resíduo. Por outro lado, polímeros biodegradáveis vêm atraindo a atenção da população como um todo, em razão dos problemas ambientais decorrentes do uso crescente de materiais poliméricos de degradabilidade baixa descartados como resíduos. Adicionalmente, quando se considera uma aplicação na área médica, torna-se necessário que os produtos sejam esterilizados, e a radiação ionizante é amplamente utilizada para a esterilização de artefatos médico-cirúrgicos. Neste trabalho, foram estudados blendas e compósitos baseados em dois polímeros comerciais: poli(e- caprolactona), PCL, e poli(ácido láctico), PLLA, e fibra de coco verde. Estes polímeros, além de biodegradáveis, são também biocompatíveis, por isso, é importante conhecer o efeito da radiação ionizante nestes materiais. As amostras foram irradiadas com raios gama proveniente de fonte de 60Co e com feixe de elétrons, com doses de radiação no intervalo de 10 kGy a 1 MGy. As amostras não irradiadas e irradiadas foram ensaiadas por diversas técnicas analíticas e de caracterização que permitiram conhecer suas propriedades de modo a viabilizar sua aplicação como precursores de artefatos médico-cirúrgicos. Não foi possível observar a influência da dose de radiação na estabilidade térmica das blendas irradiadas no intervalo de dose estudado. A adição de fibra de coco parece não influenciar significativamente a estabilidade térmica dos compósitos não irradiado e irradiados até 100 kGy. O processo de acetilação das fibras mostrou-se ineficiente na promoção da interação na interface das fibras com a matriz polimérica, conforme esperado inicialmente. Isto foi evidenciado pela ligeira redução da resistência à tração observada nas amostras dos compósitos. Apesar disso, esta redução não chega a afetar negativamente as propriedades mecânicas das blendas comparativamente com as dos compósitos. A radiação ionizante também não promoveu interação detectável entre as fibras e a matriz polimérica. Os resultados dos testes de citotoxicidade indicaram que os produtos de lixiviação dos homopolímeros, blendas e compósitos não liberaram quantidade de substâncias suficientes que provoquem morte celular significativa. O processamento térmico devido ao procedimento para a obtenção dos compósitos e o tratamento químico prévio de acetilação das fibras contribuíram para a redução da carga microbiológica. Além disso, reduzindo-se a carga microbiológica inicial, foi possível reduzir as doses necessárias para realizar a esterilização. Os resultados dos ensaios de degradabilidade enzimática e em solo simulado indicam que os materiais estudados não são afetados negativamente pelo processamento por radiação. Embora a adição das fibras tenha reduzido levemente o processo de degradação, os compósitos continuaram degradando ao longo do tempo. Os produtos fabricados utilizando os materiais estudados neste trabalho poderão ser processados por radiação até doses de 100 kGy sem prejuízo à sua biodegradabilidade. / Plastic solid waste has become a serious problem recently concerning environmental impact. In this scenario, preparation of polymers and composites based on coconut husk fiber would lead to a reduction on the cost of the final product. Additionally, it will reduce the amount of agribusiness waste disposal in the environment. In Brazil, coconut production is around 1.5 billion fruits by year in a cultivated area of 2.7 million hectares, but the coconut husk fiber has not been used much for industrial applications. Moreover, biodegradable polymers have attracted the attention of the most part of population, due to the environmental issues arising from the increasing use of polymeric materials of low degradability discharged as waste residue. Besides, when considering an application in the medical field, it is necessary that the products are sterilized and, ionizing radiation is widely used to sterilize medical and surgical devices. In this work, it was studied blends and composites based on two commercial polymers: poly (e-caprolactone), PCL, and poly (lactic acid), PLLA, and coconut fiber. Those polymers are biodegradable as well as biocompatible, so it is important to know the effect of ionizing radiation in these materials. Samples were irradiated with gamma rays from 60Co source and electron beam wtih radiation doses ranging from 10 kGy up to 1 MGy. The non-irradiated and irradiated samples were studied using several analytical techniques and characterization assays that allowed understanding their properties in order to enable their application as precursors for medical and surgical devices. Thermal stability of non irradiated and irradiated composites up to 100 kGy radiation dose is not affected significantly by the coconut fiber incorporation to the polymeric matriz. Acetylation of fibers was not effective in order to induce any interaction between fibers and polymeric matrix, as expected. That was verified by the slight reduction of stress strenght observed in the composites specimens. Besides that, this reduction did not affect negatively mechanical properties of blends compared to the composites. Ionizing radiation neither promoted detectable interaction between polymeric matrix and fibers. Citotoxicity tests indicated that lixiviation products from homopolymers, blend and composites did not release sufficient amount of substances to induce significant celular death. Thermal processing used to obtain composites and previous acetylations by chemical treatment contributed to the bioburden reduce. Furthermore, reducing initial bioburden it was possible to diminish radiation doses needed to perform sterilization. Enzymatic and soil degradation were not negatively affected by radiation processing. Even though fiber incorporation to the polymer blend slightly reduced degradation process, composites continued degrading through time. Artifacts produced by means of the materials studied here can be radiation processed with doses up to 100 kGy without prejudice of their biodegradability.

O problema do resíduo plástico vem se tornando crucial nos últimos anos no que concerne aos problemas ambientais. Neste cenário, a preparação de compósitos baseados em polímeros e fibra naturais, tais como as da casca de coco, levaria à redução do custo do produto final e a consequente diminuição da quantidade de resíduo do agronegócio descartado no meio ambiente. No Brasil, a produção anual de coco é por volta de 1,5 bilhões de frutos em uma área cultivada de 2,7 milhões de hectares. Porém, a fibra da casca do coco tem sido pouco utilizada para aplicações industriais, representando um componente importante no montante de resíduo. Por outro lado, polímeros biodegradáveis vêm atraindo a atenção da população como um todo, em razão dos problemas ambientais decorrentes do uso crescente de materiais poliméricos de degradabilidade baixa descartados como resíduos. Adicionalmente, quando se considera uma aplicação na área médica, torna-se necessário que os produtos sejam esterilizados, e a radiação ionizante é amplamente utilizada para a esterilização de artefatos médico-cirúrgicos. Neste trabalho, foram estudados blendas e compósitos baseados em dois polímeros comerciais: poli(e- caprolactona), PCL, e poli(ácido láctico), PLLA, e fibra de coco verde. Estes polímeros, além de biodegradáveis, são também biocompatíveis, por isso, é importante conhecer o efeito da radiação ionizante nestes materiais. As amostras foram irradiadas com raios gama proveniente de fonte de 60Co e com feixe de elétrons, com doses de radiação no intervalo de 10 kGy a 1 MGy. As amostras não irradiadas e irradiadas foram ensaiadas por diversas técnicas analíticas e de caracterização que permitiram conhecer suas propriedades de modo a viabilizar sua aplicação como precursores de artefatos médico-cirúrgicos. Não foi possível observar a influência da dose de radiação na estabilidade térmica das blendas irradiadas no intervalo de dose estudado. A adição de fibra de coco parece não influenciar significativamente a estabilidade térmica dos compósitos não irradiado e irradiados até 100 kGy. O processo de acetilação das fibras mostrou-se ineficiente na promoção da interação na interface das fibras com a matriz polimérica, conforme esperado inicialmente. Isto foi evidenciado pela ligeira redução da resistência à tração observada nas amostras dos compósitos. Apesar disso, esta redução não chega a afetar negativamente as propriedades mecânicas das blendas comparativamente com as dos compósitos. A radiação ionizante também não promoveu interação detectável entre as fibras e a matriz polimérica. Os resultados dos testes de citotoxicidade indicaram que os produtos de lixiviação dos homopolímeros, blendas e compósitos não liberaram quantidade de substâncias suficientes que provoquem morte celular significativa. O processamento térmico devido ao procedimento para a obtenção dos compósitos e o tratamento químico prévio de acetilação das fibras contribuíram para a redução da carga microbiológica. Além disso, reduzindo-se a carga microbiológica inicial, foi possível reduzir as doses necessárias para realizar a esterilização. Os resultados dos ensaios de degradabilidade enzimática e em solo simulado indicam que os materiais estudados não são afetados negativamente pelo processamento por radiação. Embora a adição das fibras tenha reduzido levemente o processo de degradação, os compósitos continuaram degradando ao longo do tempo. Os produtos fabricados utilizando os materiais estudados neste trabalho poderão ser processados por radiação até doses de 100 kGy sem prejuízo à sua biodegradabilidade. / Plastic solid waste has become a serious problem recently concerning environmental impact. In this scenario, preparation of polymers and composites based on coconut husk fiber would lead to a reduction on the cost of the final product. Additionally, it will reduce the amount of agribusiness waste disposal in the environment. In Brazil, coconut production is around 1.5 billion fruits by year in a cultivated area of 2.7 million hectares, but the coconut husk fiber has not been used much for industrial applications. Moreover, biodegradable polymers have attracted the attention of the most part of population, due to the environmental issues arising from the increasing use of polymeric materials of low degradability discharged as waste residue. Besides, when considering an application in the medical field, it is necessary that the products are sterilized and, ionizing radiation is widely used to sterilize medical and surgical devices. In this work, it was studied blends and composites based on two commercial polymers: poly (e-caprolactone), PCL, and poly (lactic acid), PLLA, and coconut fiber. Those polymers are biodegradable as well as biocompatible, so it is important to know the effect of ionizing radiation in these materials. Samples were irradiated with gamma rays from 60Co source and electron beam wtih radiation doses ranging from 10 kGy up to 1 MGy. The non-irradiated and irradiated samples were studied using several analytical techniques and characterization assays that allowed understanding their properties in order to enable their application as precursors for medical and surgical devices. Thermal stability of non irradiated and irradiated composites up to 100 kGy radiation dose is not affected significantly by the coconut fiber incorporation to the polymeric matriz. Acetylation of fibers was not effective in order to induce any interaction between fibers and polymeric matrix, as expected. That was verified by the slight reduction of stress strenght observed in the composites specimens. Besides that, this reduction did not affect negatively mechanical properties of blends compared to the composites. Ionizing radiation neither promoted detectable interaction between polymeric matrix and fibers. Citotoxicity tests indicated that lixiviation products from homopolymers, blend and composites did not release sufficient amount of substances to induce significant celular death. Thermal processing used to obtain composites and previous acetylations by chemical treatment contributed to the bioburden reduce. Furthermore, reducing initial bioburden it was possible to diminish radiation doses needed to perform sterilization. Enzymatic and soil degradation were not negatively affected by radiation processing. Even though fiber incorporation to the polymer blend slightly reduced degradation process, composites continued degrading through time. Artifacts produced by means of the materials studied here can be radiation processed with doses up to 100 kGy without prejudice of their biodegradability.

Com o aumento do número de animais inseminados por IATF (inseminação artificial em tempo fixo), a diminuição de custos e o incremento de índices reprodutivos têm sido os objetivos de vários grupos de pesquisa. Nos protocolos de IATF utilizados, empregam-se dispositivos de liberação sustentada de progesterona (P4), que são, em sua maioria, constituídos de um esqueleto de nylon, recoberto com uma camada de silicone com P4 . Visando a diminuição dos custos de produção e impacto ambiental, foi desenvolvido um dispositivo à base de biopolímeros. Neste estudo, foram comparados dispositivos confeccionados com uma blenda constituída de Poli-hidroxi-butirato (PHB) e Poli-&epsion;-caprolactona (PCL), com o Dispositivo Interno Bovino (DIB&reg;), utilizado como controle . No teste in vitro, utilizaram-se dois tipos de dispositivo à base de biopolímeros, com uma área superficial de 147 cm2: DISP8 (46% PHB, 46% PCL e 8% P4; n=4), DISP10 (45% PHB, 45% PCL, 10% P4; n=4) e o DIB&reg; (1 g de P4, área de 120 cm2; n=3). Os testes in vitro foram conduzidos segundo especificações da USP 23, em um dissolutor de comprimidos, empregando-se uma mistura de álcool/água (60/40) como meio de difusão. Amostras do meio foram colhidas aos 2 min., 2, 4, 8, 12, 24, 48, 60, 72, 84 e 96 h. Os teores de P4 foram dosados por espectrofotometria, em 244 nm de comprimento de onda. Realizaram-se as comparações 3 a 3 dos coeficientes angulares das retas obtidas pela regressão das concentrações acumuladas de P4, em função da raiz quadrada do tempo. As médias e respectivos erros-padrão dos coeficientes angulares foram de 677,39 ± 16.13 µg/cm2/t1/2 para o DIB&reg;, 566,17 ± 3.68 µg/cm2/t1/2 para o Disp8 e 774,63 ± 45.26 µg/cm2/t1/2 para o Disp10. Houve diferença entre o DISP8 e o DISP10 (p< 0,05), mas ambos não diferiram do DIB. Para análise das quantidades liberadas por dia de teste in vitro, consideraram-se 4 períodos: 0-24, 24-48, 48-72 e 72-96 h. Houve interação entre tratamento e tempo (p=0,0024). Nas primeiras 24 horas, o DISP8 liberou significativamente menos P4 do que o DISP10 e o DIB&reg;, cujas liberações não diferiram entre si. No intervalo entre 24 e 48h, o DISP 10 liberou significativamente mais P4 do que o DIB&reg;. O DISP8 liberou uma quantidade de P4 intermediária e não se diferenciou significativamente nem do DIB&reg; e nem do DISP10. No intervalo entre 48 e 72h a quantidade de P4 liberada pelo DISP10 foi significativamente maior do que a do DIB&reg; e a do DISP8, que não diferiram entre si. No intervalo entre 72 e 96h, o DISP10 liberou significativamente mais P4 do que o DIB&reg; e o DISP8 liberou uma quantidade intermediária que não diferiu do DIB&reg; nem do DISP10. No teste in vivo, seis vacas mestiças ovariectomizadas receberam DIB (n=4) ou DISP8 (n=8), em um delineamento alternado, com seqüência não balanceada (cross-over), adicionado de medidas repetidas no tempo, referentes aos 16 dias de colheita das amostras de sangue. As amostras foram analisadas por rádio-imuno-ensaio, em fase sólida, utilizando-se &quotkit&quot comercial da DPC (Diagnostics Products Corporation). As concentrações de pico foram atingidas 4 h após a colocação dos dispositivos e este foi o único momento em que as concentrações plasmáticas de P4 diferiram segundo dispositivo (11,45±1,96 vs 9,23±1,15 ng/mL, respectivamente para DIB e DISP8; p= 0,027). No dia 8 do ensaio, as concentrações plasmáticas de P4 proporcionadas pelo DIB e pelo DISP8 foram respectivamente 2,44±0,09 e 1,89±0,13 ng/mL (p=0.58). Ambos dispositivos mantiveram teores de P4 superiores a 1 ng/mL, durante os 16 dias do teste in vivo. Concluiu-se que os dispositivos confeccionados com a blenda dos biopolímeros PHB/PCL, podem liberar P4 de maneira sustentada, tanto quanto os que empregam silicone em sua fabricação. / With the increase in the number of animals inseminated by TAI (timed artificial insemination) the decrease of costs and the improvement of reproductive performance are the goals of several research groups. Progesterone devices which are majority constituted of a nylon skeleton covered with a silicone layer with P4, are used in TAI protocols. Aiming the decrease of the production costs and the environmental impact, was a new device developed with biopolymers matrix. In this study, were compared a blend of Poli-hidroxi-butirate (PHB) and poli-?-caprolactone (PCL) device with the Bovine Internal Device (DIB&reg;). In the in vitro test, two kinds of the new device with a superficial area of 147 cm2: DISP8 (46% PHB, 46% PCL and 8% P4; n=4), DISP10 (45% PHB, 45% PCL, 10% P4; n=4) and DIB&reg; (1 g of P4, area of 120 cm2; n=3). The in vitro tests were led following USP 23 specifications in a drug dissolutor in alcohol/water (60/40) solution as a diffusion medium. Samples were collected at 2 min., 2, 4, 8, 12, 24, 48, 60, 72, 84 and 96 hours. Progesterone concentrations were estimated by spectrophotometry at UV 244 nm wavelenght. Comparisons 3 by 3 of the angular coefficients of the straight lines obtained by the regression of the accumulated P4 concentrations in function of the square root of time were performed. The averages and respective standard-errors of the angular coefficients were 677,39 ± 16.13 µg/cm2/t1/2 to DIB&reg;, 566,17 ± 3.68 µg/cm2/t1/2 to Disp8 and 774,63 ± 45.26 µg/cm2/t1/2 to Disp10. Difference were observed between DISP8 and DISP10 (p< 0.05) but both did not differ to DIB&reg;. Four periods were considered for analysis of the amounts released per day of in vitro test: 0-24, 24-48, 48-72 and 72-96 hours. Interaction between treatment and time was observed (p=0.0024). In the first 24 hours DISP8 released significantly less P4 than DISP10 and DIB&reg; but the lathers did not differ from each other. In the interval between 24 and 48 hours DISP10 released significantly more P4 than DIB&reg;. The device DISP8 released an intermediary concentration of P4 and was similar to DIB&reg; and to DISP10. In the interval between 48 and 72 hours the progesterone concentration released by DISP10 was significantly higher than DIB&reg; and DISP8 but lathers did not differ from each other. In the interval between 72 and 96 hours DISP10 released significantly more P4 than DIB&reg; while DISP8 released an intermediary amount which did not differ to DIB&reg; or to DISP10. In the test in vivo test, six ovariectomized beef cows received the devices DIB&reg; (n=4) or DISP8 (n=8) in an alternated delineation in a nom balanced sequence (cross-over) added of repeated measures in time, related to the 16 days of blood samples collects. Progesterone concentration from these samples were measured by radioimmunoassay in solid phase using the commercial kit from DPC (Diagnostics Products Corporation). The peak of the progesterone concentrations were observed 4 hours after the devices insertion and this was the unique moment in which plasmatic progesterone concentrations differed depending on device (11,45 ± 1,96 vs 9,23 ± 1,15 ng/mL, respectively for DIB and DISP8; p= 0,027). After 8 days from the device insertion plasmatic progesterone concentrations provided by DIB and DISP8 were respectively 2,44 ± 0,09 and 1,89 ± 0,13 ng/mL (p=0.58). Both devices kept the progesterone concentration higher than 1 ng/mL during the 16 days of the in vivo test. In conclusion, the devices made with biopolymers blends of PHB/PCL can release sustained P4 comparable with silicone matrix.

Les opérations chirurgicales pour le traitement des défauts de soutènement d'organes dans les pays industrialisés sont des actes de plus en plus fréquents, et requièrent l'implantation de plus d'un million de prothèses par an. Même si l'usage des prothèses de soutènement a permis de diminuer les complications postopératoires, les taux de réinterventions restent très élevés. Ces travaux présentent différentes stratégies permettant d'apporter de nouvelles propriétés à des treillis en polypropylène, afin d'améliorer leur résistance à l'infection et de permettre leur suivi postopératoire en IRM. Des treillis anti-infectieux sont développés en enrobant les filaments de treillis d'un réservoir de polymère dégradable et biocompatible contenant des agents anti-infectieux, par une technique de pulvérisation à l'aide d'un aérographe. L'association ofloxacine – rifampicine incorporée présente une excellente activité antibactérienne in vitro, et la cinétique de libération prolongée des agents actifs permet d'inhiber la contamination des treillis pendant au moins 72 heures. Les techniques de stérilisation par rayonnement Gamma n'impactent ni la stabilité des agents actifs, ni l'efficacité antibactérienne des treillis anti-infectieux.Afin de permettre une visualisation en IRM des treillis implantés, des polymères ont été synthétisés par greffage d'agent de contraste (DTPA-Gd) sur de la poly(ε-caprolactone) (dégradable) et du poly(acrylate de méthyle) (biostable). Après enrobage des prothèses par ces polymères, le rehaussement du signal induit par la présence du gadolinium permet de visualiser les prothèses à la fois in vitro et in vivo sur différents types d'appareils d'IRM. La stabilité de l'agent de contraste est suffisante pour pouvoir visualiser les treillis pendant plusieurs mois, quelle que soit la technique de stérilisation utilisée. / Soft tissue reinforcement surgical operations in industrial countries are common and require annually at least one million of prostheses for treating this problem. Even if meshes used for organ prolapse surgical procedures allow decreasing postoperatory complications, reinterventions ratio is still relevant. This work present several strategies to bring new properties to polypropylene meshes in order to improve their resistance to infection and enable their postoperative MRI follow-up. Anti-infective meshes are developed by coating the filaments of the meshes with an antibiotics drug reservoir based on degradable and biocompatible polymers, using an airbrush system. Dual ofloxacin-rifampicin antibiotics incorporation on these coated meshes shows an excellent antibacterial activity in vitro and sustained release of the drugs can inhibit meshes contamination for at least 72 hours. Sterilization procedures using Gamma-ray irradiation impact neither the drugs stability nor the anti-infective meshes activity. In order to visualize by Magnetic Resonance Imaging (MRI) meshes after implantation, a contrast agent (DTPA-Gd) is covalently grafted onto the polymeric backbone of poly(ε-caprolactone) (degradable) or poly(methyl acrylate) (biostable). Meshes were coated with these new polymers and MR signal enhancement induced by the presence of gadolinium allows the visualization of the meshes in vitro and in vivo with several MR equipments. Coated meshes are visible during several months, whatever the sterilization procedures, showing the stability of the contrast agent.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-04-19T11:42:18Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação Natércia Antunes Gonçalves.pdf: 4208190 bytes, checksum: b60c1953389fb9ccc50987db955906d5 (MD5) / Made available in DSpace on 2016-04-19T11:42:19Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação Natércia Antunes Gonçalves.pdf: 4208190 bytes, checksum: b60c1953389fb9ccc50987db955906d5 (MD5) Previous issue date: 2015-08-28 / FACEPE / O poli(ε-caprolactona) (PCL) é um poliéster biocompatível, biodegradável e semicristalino utilizado na confecção de artefatos médico-farmacêuticos, especialmente como suporte para cultivo de células e tecidos. Por outro lado, sua hidrofobicidade e baixas taxas de hidrólise in vivo impedem a expansão do uso destes polímeros em aplicações biológicas. Nesta pesquisa, empregamos três estratégias na tentativa de aumentar a taxa de hidrólise da PCL: a) preparação do material em morfologia fibrilar, para aumentar a superfície de contato com o meio; b) irradiação com raios gama, para induzir dano molecular e acelerar a hidrólise; e c) blenda com o polímero hidrofílico e lixiviável poli(óxido de etileno) (PEO), para aumentar a molhabilidade e permitir maior percolação da água. Tapetes de PCL, apresentando nanofibras com diâmetros menores que 100nm e de microfibras com diâmetros entre 1,9 e 7,5μm da blenda PCL/PEO 10% m/m foram preparados pela técnica de eletrofiação, irradiados com raios gama em doses de 25 e 50kGy e submetidos à hidrólise por submersão em tampão fosfato salino (PBS) pH 7,4 a 37 0C. Para comparação, filmes de PCL e da blenda de PCL/PEO foram confeccionados por derrame em solução (film casting) e submetidos ao mesmo tratamento. Nada se pode afirmar sobre as mudanças de Massa Molar Viscosimétrica Média (Mv) em filmes de PCL irradiados, pois não foi possível observar nem o efeito de cisão, nem reticulação da cadeia principal. A irradiação gama não influenciou nas propriedades térmicas dos filmes de PCL e os cálculos de energia de ativação para reações de decomposição térmica evidenciaram que filmes de PCL têm boa estabilidade térmica. Ensaios espectrométricos no Infravermelho com Transformada de Fourier (FTIR) e difratométricos de raios X dos filmes de PCL não foi possível observar mudanças significativas de estrutura molecular ou cristalinidade com a irradiação gama. As estratégias adotadas para melhorar a degradação hidrolítica do PCL funcionaram. Blendas de PCL/PEO (10% m/m) apresentaram taxa de degradação hidrolítica maiores do que as amostras de PCL, tanto na forma de tapetes microfibrilares eletrofiados como na forma de filmes espessos. Sendo a primeira com taxa de degradação mais acentuada. A irradiação gama exerce influência significativa na degradação hidrolítica apenas em blendas PCL/PEO na forma de filmes. A degradação hidrolítica dos filmes de PCL se mostrou muito lenta, não sendo possível observar diferenças significativas entre amostras irradiadas e não irradiadas. / Poly (ε-caprolactone) (PCL) is a biocompatible, biodegradable, semicrystalline polyester used in medical-pharmaceutical devices, specially as scaffolds in cell and tissue culture. Nevertheless, its hydrophobicity and low in vivo hydrolysis rates are obstacles to the expansion of its use in biological applications. In this work, we designed three strategies to address PCL hydrophobicity issues: a)prepare electrospun fibers to enhace contact surface with aqueous media; b)irradiation with gamma rays to induce molecular damage and increase hydrolysis rate; and c) blending with the hydrophilic, leacheble polymer poly(ethylene oxide) (PEO), in order to increase wettability and allow larger water percolation rates. Mats of PCL electrospun nanofiber with less than 100nm in diameter; and of electrospun PCL/PEO (10%wt) blend microfibers presenting diameters in the range of 1.9 - 7.5 μm were irradiated with gamma rays in 25 and 50 kGy dose and submitted to in vitro hydrolysis in phosphatebuffered saline (PBS) solution, pH 7,4 at 37 0C. PCL and PCL/PEO (10%wt) films were also prepared by film casting and treated in the same way, for comparison. Nothing can be said about mass changes Viscosity Average Molar Mass (Mv) in irradiated PCL films because it was not possible to observe nor the effect of spin-off, or crosslinking of the backbone. Good thermal stability was also evidenced by calculations of activation energy for thermal degradation of PCL. Fourier Transform Infrared espectrometry and X-ray difractometry data did not evidence significant changes in molecular structure or crystallitiny of PCL after irradiation. Strategies to improve PCL in vitro hydrolysis degradation rate were successful. Blends of PCL/PEO (10% wt) presented higher hydrolysis rates than PCL samples, either in mat fibers or film forms. Hydrolysis degradation of PCL films was very slow, and no differences between non irradiated or irradiated samples were observed.

<p>In this work, an in-depth analysis of crystalline characteristics has been performed for a unique set of strictly monodisperse poly-ε-caprolactone (PCL) oligomers. The molecules have different sets of end groups with various degrees of bulkiness and hydrogen bonding potential, affecting their aptitude to pack in ordered crystal structures. The oligomers also have different numbers of repeating units (<em>n </em>= 2-64), affecting the degree to which end groups influence overall molecular characteristics. The presence of bulky end groups leads to an innate confinement effect on crystallisation which in turn makes it possible to utilize the set of PCL oligomers to study confined space crystallisation. Confined space crystallisation is explored as a route to gain further understanding about the early metastable phases in crystal formation.</p><p> </p><p>The monodisperse nature of the samples made it possible to collect very precise small-angle and wide-angle X-ray scattering data (SAXS and WAXS) as well as calorimetric data. Computer modeling studies were performed to support experimental findings. It was shown that end groups strongly affected crystallisation features for the shorter oligomers (<em>n </em>≤ 8) but to a lesser extend for the longer oligomers (<em>n </em>≥ 16). The presence of a bulky end group at one end of an oligomer could inhibit the formation of hydrogen bonds on the other end. Short oligomers (<em>n</em> = 8) with OH-end groups exhibited novel packing characteristics. At one isothermal crystallisation temperature the molecules exhibited not only lamellar ordering but also an additional, likely rectangular or slanted, ordering. The sample was packed in a unique structure with molecular chains lying parallel but not aligned head to head with each other. At a higher crystallisation temperature the molecules packed in a double layered structure and at an even higher temperature in a typical non-folded but tilted single-molecular layer pattern.</p><p> </p><p>Unit cell determination was performed for a short oligomer with two bulky end groups, showing the existence of a tetragonal unit cell with different dimensions than the orthorhombic unit cells previously reported for linear PCL without end groups. To gain greater insight into the earliest stages of molecular packing, in situ WAXS measurements were performed using a synchrotron radiation beam and measuring data each 12 s whilst very slowly going from melt to isothermal crystallisation. It was shown that the crystal unit cell was distorted during the first minutes of slow crystallisation, which might either represent a metastable phase or else a highly distorted orthorhombic phase.</p>

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-10-18T18:56:51Z No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O.pdf: 1545312 bytes, checksum: f915686f1b1663c40d8c1dba1f335b6d (MD5) / Rejected by Sheila Dias (sheila.dias@pucrs.br), reason: Devolvido devido ? falta da capa institucional no arquivo PDF. on 2018-10-19T12:03:09Z (GMT) / Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-10-19T20:35:58Z No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O_PUCRS.pdf: 1572906 bytes, checksum: 81eb2ad136f458f673745debe4a6fa13 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-10-22T11:20:21Z (GMT) No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O_PUCRS.pdf: 1572906 bytes, checksum: 81eb2ad136f458f673745debe4a6fa13 (MD5) / Made available in DSpace on 2018-10-22T11:30:50Z (GMT). No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O_PUCRS.pdf: 1572906 bytes, checksum: 81eb2ad136f458f673745debe4a6fa13 (MD5) Previous issue date: 2017-10-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Glyphosate is the most widely used herbicide in the world, due to its broad spectrum of action. But there is a need for reduction measures in its application, due to the risks associated with contamination of water and the environment. The development of controlled release systems appears as an alternative to minimize the application of this herbicide. This work aimed at the preparation of glyphosate-containing Poly (?-caprolactone) (PCL) microspheres. These were characterized as to their morphology, structure, physicochemical properties, and a bioassay was carried out to evaluate their use in rice cultivation, in order to create a possible alternative for the use of these herbicides in plantations. The PCL / glyphosate microspheres produced by the multiple emulsion technique and solvent evaporation were in the form of solid beads with mean sizes of 3 ?m ? 0.6 ?m. It was possible to incorporate 9.3% glyphosate in relation to the polymer mass in the formed particles, revealing an efficiency of incorporation IE of 30.9%. From the techniques used to quantify the incorporated glyphosate (UVvis, TGA and CHN), it can be stated that with the increase of glyphosate concentration in the formulation there is an increase in its IE. On the other hand, this increase leads to a decrease in the average size of the microspheres. The release of the herbicide from the microspheres was evidenced by bioassays, and in the assessment of the glyphosate release profile of the microspheres, it can be seen that approximately 17% of the herbicide was released into the medium, 0.01 M CaCl2 solution at room temperature, after 360 minutes of testing. This study allowed to affirm that the theoretical model described by Korsmeyer-Peppas is adequate to characterize the phenomenon of transport of glyphosate release from the microspheres, revealing an anomalous transport not governed by Fick diffusion. / O glifosato ? o herbicida mais utilizado no mundo, devido ao seu amplo espectro de a??o. Por?m existe a necessidade de medidas de redu??o na sua aplica??o, devido aos riscos associados ? contamina??o da ?gua e do meio ambiente. O desenvolvimento de sistemas de libera??o controlada surge como uma alternativa para minimizar a aplica??o deste herbicida. Este trabalho teve como objetivo a prepara??o de microesferas de Poli (?-caprolactona) (PCL) contendo glifosato. Estas foram caracterizadas quanto a sua morfologia, estrutura, propriedades f?sicoqu?micas, e ainda, realizou-se um bioensaio para a avalia??o do seu uso na cultura do arroz, a fim de criar uma poss?vel alternativa para o uso destes herbicidas em planta??es. As microesferas de PCL/glifosato produzidas atrav?s da t?cnica de emuls?o m?ltipla e evapora??o do solvente apresentaram a forma de esferas s?lidas com tamanhos m?dios de 3 ?m ? 0,6 ?m. Foi poss?vel incorporar 9,3% de glifosato em rela??o ? massa de pol?mero nas part?culas formadas, revelando uma efici?ncia de incorpora??o (EI) de 30,9%. A partir das t?cnicas utilizadas para quantifica??o do glifosato incorporado (UVvis, TGA e CHN), pode-se afirmar que com o aumento da concentra??o de glifosato na formula??o existe um aumento de sua EI. Por outro lado este aumento acarreta na diminui??o no tamanho m?dio das microesferas. A libera??o do herbicida das microesferas foi evidenciada atrav?s de bioensaios, e na avalia??o do perfil de libera??o do glifosato das microesferas, pode-se constatar que aproximadamente 17% do herbicida foi liberado para o meio, solu??o de CaCl2 0,01 M em temperatura ambiente, ap?s transcorridos 360 minutos de ensaio. Este estudo permitiu afirmar que o modelo te?rico descrito por Korsmeyer-Peppas ? adequado para caracterizar o fen?meno de transporte de libera??o do glifosato das microesferas, revelando um transporte an?malo n?o governado pela difus?o de Fick.

Although their numbers are in the minority in the general offender population, psychopathic offenders are responsible for a significant proportion of the most serious offenses committed (Hare, 1993, 2003). A particularly serious concern is that they are a notoriously challenging population to work with clinically and effectively treat (Polaschek, 2014; Salekin, 2002). Recent findings suggest, however, that psychopathic offenders are able to demonstrate treatment changes that translate into reduced recidivism (Olver & Wong, 2009). A greater understanding of the etiology and treatment responses of psychopathic offenders is needed (Salekin, 2002). Consequently, the present archival dissertation program of research aimed to explore the etiological and treatment response variables of psychopathic and nonpsychopathic sexual offenders in a sample of 302 federal inmates. The influence of psychopathy, risk, and treatment change as it pertained to rates of long-term recidivism was explored. Further, to add to the growing body of literature suggesting that psychopathy may be best conceptualized as different subtypes, cluster analysis was utilized to examine the potential of subtypes of psychopathic offenders who respond differently to treatment. Finally, it has been proposed that psychopathic traits may be adaptive and thus, treatment resistant (Harris & Rice, 2006). Therefore, the relationship between treatment response and evolutionarily relevant variables was explored. Phase one results were consistent with past findings (Olver & Wong, 2009; Olver, Stockdale, & Wormith, 2011) where psychopathic offenders demonstrated higher rates of treatment drop out, but the majority did complete treatment in the current sample. Furthermore, although psychopathic offenders amassed fewer risk relevant treatment gains than their nonpsychopathic counterparts on the whole, there was a group of psychopathic individuals whose therapeutic gains were high and resulted in similar recidivism rates to the nonpsychopathic offenders. Finally, after controlling for comprehensive baseline risk level and treatment change, the PCL-R no longer significantly predicted violent or sexual recidivism. Moreover, treatment change was associated with reduced recidivism, regardless of risk level or psychopathy. This provided support for Wong and colleagues (2012) two component model for the treatment of psychopathy, wherein if service providers can manage and respond to the specific responsivity issues with psychopathic individuals and increase their engagement in treatment, then risk relevant changes that result in lower recidivism are possible. In phase two, two subtypes of psychopathic offenders were found using PCL-R facet scores that were consistent with the primary and secondary distinction. The primary subtype demonstrated a high degree of the classic psychopathic personality traits, whereas the secondary type had more behavioral and lifestyle traits and to a lesser degree, the callous personality. In terms of external variables, the secondary group had slightly higher risk levels, treatment change, and rates of violent reoffending, but the differences failed to reach statistical significance. Finally, in phase three, there was evidence for psychopathy’s relationship with proxies for adaptation, but the evidence for adaptation had little bearing on treatment response. Furthermore, the adaptive markers were largely accounted for by the general antisociality of psychopathy, rather than the psychopathic personality itself. The results were then integrated and implications for the future treatment of psychopathic offenders were discussed.