Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-06-25T13:24:34Z No. of bitstreams: 1 Dissserta??o final_Lucas Weber Dias.pdf: 2263503 bytes, checksum: ea9c29b6b538c56ea795610f7bc5a808 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-06-29T13:30:33Z (GMT) No. of bitstreams: 1 Dissserta??o final_Lucas Weber Dias.pdf: 2263503 bytes, checksum: ea9c29b6b538c56ea795610f7bc5a808 (MD5) / Made available in DSpace on 2018-06-29T13:38:08Z (GMT). No. of bitstreams: 1 Dissserta??o final_Lucas Weber Dias.pdf: 2263503 bytes, checksum: ea9c29b6b538c56ea795610f7bc5a808 (MD5) Previous issue date: 2017-08-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The main function of the packaging is to protect the cosmetic from the external environment, avoiding undesirable changes in the product that is contained inside, and thus indispensable for its storage and transpotation. However, its disposal improperly generates a large volume of solid waste, which is directly related to the environmental impact. One of the alternatives to minimize this impact is the use of packages made from biodegradable polymeric films based on polyacrylic acid (PLA), poly (lactic acid ? co- glycolic acid) (PLGA) and polycaprolactone (PCL), blends of theses polymers and incorporation of Zeolites 13x. The thermal, mechanical optical, water vapor barrier and degradation time in saline solution of polymeric systems are evaluated for application as cosmetic packaging. The technique used for the preparation of the polymer films was that of Solvent Casting. The polymer films were characterized by the techniques of UV-Vis Spectrophotometry, Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Scsannig Electron Microscopy (SEM), transparency, water vapor permeability, mechanical assay and absorption spectroscopy atomic. The transmittance results showed that the PCL and PLA blends showed greater blockage to the passage of radiation (190 - 1100nm) and water vapor permeability. The incorporation of PLA or PLGA to the pure PCL resulted in material with batter thermal properties, but more rigid and brittle, not modifying the degradation process until 120 days of incubation. The incorporation of 15% Zeolite 13x into the PCL/PLA blends did not significantly modify the properties evaluated. / As embalagens t?m como principal fun??o, proteger o cosm?tico do meio externo, evitando que ocorram altera??es indesej?veis no produto que est? contido no seu interior, sendo assim indispens?vel para o seu armazenamento e transporte. Por?m, o seu descarte de forma inadequada gera um grande volume de res?duos s?lidos, que est? diretamente relacionado com o impacto ambiental. Uma das alternativas para minimizar este impacto ? a utiliza??o de embalagens confeccionadas a partir de pol?meros biodegrad?veis. Desta maneira, o presente trabalho tem como objetivo a prepara??o e caracteriza??o de filmes polim?ricos biodegrad?veis baseados em Poli ? ?cido l?ctico (PLA), Poli (?cido l?ctico ? co- ?cido glic?lico) (PLGA) e Policaprolactona (PCL), blendas destes pol?meros e incorpora??o de Ze?litas 13x. S?o avaliadas as propriedades t?rmicas, mec?nicas, ?pticas, de barreira a vapor de ?gua e o tempo de degrada??o em solu??o salina dos sistemas polim?ricos, visando aplica??o como embalagem para cosm?ticos. A t?cnica utilizada para a prepara??o dos filmes polim?ricos foi a de Solvent Casting. Os filmes polim?ricos foram caracterizados pelas t?cnicas de Espectrofotometria UV-Vis, Calorimetria Explorat?ria Diferencial (DSC), An?lise Termogravim?trica (TGA), Microscopia Eletr?nica de Varredura (MEV-FEG), transpar?ncia, permeabilidade a vapor de ?gua, ensaio mec?nico e Espectroscopia de absor??o at?mica. Os resultados de transmit?ncia mostraram que a blenda de PCL e PLA apresentou maior bloqueio ? passagem de radia??o (190 nm ? 1100 nm) e ? permeabilidade de vapor de ?gua. A incorpora??o de PLA ou PLGA ao PCL puro resultou num material com melhores propriedades t?rmicas, por?m mais r?gido e quebradi?o, n?o modificando o processo de degrada??o at? 120 dias de incuba??o. A incorpora??o de 15% Ze?lita 13x ? blenda de PCL/PLA n?o modificou significativamente as propriedades avaliadas.

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.

Neste trabalho, desenvolvemos blendas de polímeros biodegradáveis e polímeros condutores com objetivo de avaliar o potencial destes materiais para uso em aplicações biomédicas. O polímero condutor polipirrol (PPY) e os polímeros biodegradáveis poli(-caprolactona) (PCL) e poli(3-hidróxido de butirato) (P3HB) foram escolhidos devido à comprovada biocompatibilidade apresentada por cada um destes três polímeros. O PPY foi sintetizado via polimerização em emulsão, utilizando-se o dodecil sulfato de sódio (SDS) como surfactante e o FeCl3 como oxidante e dopante. A morfologia do polímero obtido foi estudada por microscopia eletrônica de varredura e por microscopia eletrônica de transmissão. O PPY se apresentou como agregado de partículas aproximadamente esféricas, com dimensões da ordem de 80 a 200nm. Verificamos que ocorre uma redução significativa do tamanho das partículas formadas, proporcionalmente ao aumento da concentração de SDS. Os ensaios de microanálise por energia dispersiva (EDS) e de espectroscopia de absorção no infravermelho (FTIR) demonstraram a incorporação de SDS ao PPY, o SDS atuando como contra-íon deste polímero. Isto está de acordo com os resultados de condutividade elétrica obtidos para o polímero sintetizado sem o SDS (1.9S/cm) e com 100mM de SDS (23.3S/cm). A seguir, foram preparadas as blendas, dispersando-se as partículas de PPY em matrizes poliméricas de PCL ou de P3HB, sendo a morfologia destas blendas estudada por microscopia eletrônica de varredura. Em blendas de PCL, as partículas de PPY localizam-se principalmente entre os esferulitos da matriz, devido ao processo de cristalização da PCL. Diferentemente, nas blendas de P3HB estas partículas agruparam-se em várias regiões, e não foram localizadas na superfície dos filmes produzidos. A condutividade elétrica obtida para as blendas de PCL e de P3HB, ambas contendo 15% de PPY, foi respectivamente, 20.8mS/cm e 5.5mS/cm. Esta diferença de valores encontrada, parece estar relacionada à formação de uma rede de partículas de PPY na matriz de PCL. Medidas do ângulo de contato da superfície das blendas de PCL e de P3HB mostraram que elas se tornam progressivamente mais hidrofílicas com o aumento da proporção de PPY. Os resultados obtidos neste trabalho indicam que estas blendas podem ser biocompatíveis, justificando o prosseguimento de novos estudos envolvendo métodos de ensaio in vivo, para uma avaliação mais adequada. / Polymers blends making use of two biodegradable polymers, and a conductive one, were synthesized and characterized in the laboratory, aiming at the development of a new material that would combine adequate properties of biodegradability and electrical conductivity. As such, these blends would be suitable for making special devices to be used in biomedical applications. The well known conducting polymer polypyrrole (PPY), was synthesized, then blended with either poly(-caprolactone) (PCL) and poly(3-hydroxybutyrate) (P3HB), both biodegradable, therefore biocompatible, polymers. PPY particles were obtained along the polymerization route, in which SDS (sodium dodecyl sulfate) acted as a surfactant and FeCl3 as the oxidizing and dopant agent. The PPY samples were characterized by scanning and transmission electron microscopy, as spherical particles having 80-200nm in diameter; it was found that final particle size was inversely related to the concentration of SDS used in the synthesis pathway. The particles were further characterized by energy dispersive microanalysis (EDS) and infrared spectroscopy (FTIR), to demonstrate incorporation of the SDS into the PPY. SDS actually behaves as a counterion of the polymer, according to electrical conductivity results of polymer synthesized without SDS (1.9S/cm) or with 100mM SDS (23.3S/cm). This PPY polymer was then blended with either PCL or PHB matrices. The microstructure of the two resulting blends, as investigated by scanning electron microscopy demonstrates PPY particles mostly located within the interstices of spherulites in the PCL blends, whereas in P3HB blends, they formed irregular patches along the matrix. Electrical conductivity for blends containing 15% PPY were: 20.8mS/cm for PCL blends and 5.5mS/cm for P3HB blends. It can be concluded therefore, that these different values obtained for electrical conductivity were related to the particle distribution within the two matrices. Also, hydrophilic properties of the two blends, according to contact angle measurements, seem to correspond to the content of PPY.

Devido ao crescente interesse em polímeros biodegradáveis, muitos estudos têm sido realizados a fim de se obter polímeros biodegradáveis com melhores propriedades mecânicas e de processamento. O poli(3-hidroxibutirato) (PHB) tem sido apresentado como um substituto para polímeros não-biodegradáveis em aplicações comerciais. Porém, sua elevada cristalinidade, instabilidade térmica e alto custo de produção são problemas que dificultam sua comercialização. Uma alternativa para modificá-lo e melhorar suas propriedades mecânicas é através de reações de transesterificação com poli(?-caprolactona) (PCL), um poliéster sintético, também biodegradável e com alto potencial para uso como biomaterial. Neste trabalho, realizou-se a extrusão reativa de blendas de PHB e PCL e o copolímero obtido foi caracterizado por ensaios de solubilidade, calorimetria exploratória diferencial (DSC), espectroscopia no infravermelho por transformada de Fourier (FTIR), espectrometria de ressonância magnética nuclear de hidrogênio (RNM-1H) e de carbono (RNM-13C). Os resultados indicaram que houve modificação do PHB resultando no copolímero PHB-co-PCL, que apresentou menor cristalinidade que os homopolímeros de partida. Com o PHB-co-PCL, foram feitas medidas de viscosidade e ensaios de eletrofiação, variando-se os parâmetros do processo e da solução. As análises por microscopia eletrônica de varredura (MEV) apontaram formação de fibras lisas e uniformes com diâmetros médios entre 900 a 1200 nm. Análise de viabilidade celular confirmou que o material não é citotóxico, favorecendo sua aplicabilidade em mantas porosas na engenharia de tecidos. / Due to the increasing interest in biodegradable polymers, many studies have been conducted in order to obtain biodegradable polymers with improved mechanical and processing properties. The poly(3-hydroxybutyrate) (PHB) has been proposed as an ideal substitute for non-biodegradable polymers in commercial applications. However, its high crystallinity, thermal instability and high production costs are problems that have limited its commercialization. An alternative to modify it and improve its mechanical properties is through transesterification reactions with poly(?-caprolactone) (PCL), a synthetic polyester, also biodegradable and with high potential for use as a biomaterial. In this work, reactive extrusion of PHB/PCL blend was carried out, and the copolymer was characterized by solubility tests, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), hydrogen (1H-NMR) and carbon (13C-NMR) nuclear magnetic resonance spectroscopies. The results indicated that PHB was modified, resulting in the copolymer PHB-co-PCL, showing lower crystallinity than the homopolymers. Viscosity measurements of PHB-co-PCL solutions were performed and electrospinning tests were carried out under different conditions. The scanning electron microscopy analysis (SEM) indicated the formation of smooth and uniform fibers, with average diameter between 900-1200 nm. Cell viability analysis confirmed that the material is not cytotoxic, favoring its applicability for the production of porous fiber mats in tissue engineering.

Devido ao crescente interesse em polímeros biodegradáveis, muitos estudos têm sido realizados a fim de se obter polímeros biodegradáveis com melhores propriedades mecânicas e de processamento. O poli(3-hidroxibutirato) (PHB) tem sido apresentado como um substituto para polímeros não-biodegradáveis em aplicações comerciais. Porém, sua elevada cristalinidade, instabilidade térmica e alto custo de produção são problemas que dificultam sua comercialização. Uma alternativa para modificá-lo e melhorar suas propriedades mecânicas é através de reações de transesterificação com poli(?-caprolactona) (PCL), um poliéster sintético, também biodegradável e com alto potencial para uso como biomaterial. Neste trabalho, realizou-se a extrusão reativa de blendas de PHB e PCL e o copolímero obtido foi caracterizado por ensaios de solubilidade, calorimetria exploratória diferencial (DSC), espectroscopia no infravermelho por transformada de Fourier (FTIR), espectrometria de ressonância magnética nuclear de hidrogênio (RNM-1H) e de carbono (RNM-13C). Os resultados indicaram que houve modificação do PHB resultando no copolímero PHB-co-PCL, que apresentou menor cristalinidade que os homopolímeros de partida. Com o PHB-co-PCL, foram feitas medidas de viscosidade e ensaios de eletrofiação, variando-se os parâmetros do processo e da solução. As análises por microscopia eletrônica de varredura (MEV) apontaram formação de fibras lisas e uniformes com diâmetros médios entre 900 a 1200 nm. Análise de viabilidade celular confirmou que o material não é citotóxico, favorecendo sua aplicabilidade em mantas porosas na engenharia de tecidos. / Due to the increasing interest in biodegradable polymers, many studies have been conducted in order to obtain biodegradable polymers with improved mechanical and processing properties. The poly(3-hydroxybutyrate) (PHB) has been proposed as an ideal substitute for non-biodegradable polymers in commercial applications. However, its high crystallinity, thermal instability and high production costs are problems that have limited its commercialization. An alternative to modify it and improve its mechanical properties is through transesterification reactions with poly(?-caprolactone) (PCL), a synthetic polyester, also biodegradable and with high potential for use as a biomaterial. In this work, reactive extrusion of PHB/PCL blend was carried out, and the copolymer was characterized by solubility tests, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), hydrogen (1H-NMR) and carbon (13C-NMR) nuclear magnetic resonance spectroscopies. The results indicated that PHB was modified, resulting in the copolymer PHB-co-PCL, showing lower crystallinity than the homopolymers. Viscosity measurements of PHB-co-PCL solutions were performed and electrospinning tests were carried out under different conditions. The scanning electron microscopy analysis (SEM) indicated the formation of smooth and uniform fibers, with average diameter between 900-1200 nm. Cell viability analysis confirmed that the material is not cytotoxic, favoring its applicability for the production of porous fiber mats in tissue engineering.

The first polysulfenamides were synthesized with S-N and N-S-N bonds along the backbone. We demonstrated that sulfenamides were stable in polar protic and aprotic solvents, but degraded rapidly when exposed to acidic conditions. Microparticles were fabricated from polysulfenamides with S-N bonds, their surfaces were readily functionalized, and they were internalized by cells allowing for intracellular delivery of their cargo. These microparticles were also stable at physiological pH, degraded under acidic conditions, and possessed minimal toxicity towards cells. This work demonstrated that polysulfenamides form the basis for a new set of polymers for drug delivery that greatly differ from prior work in this field. New biodegradable polymers with N-S-N bonds along the backbone were synthesized. These were the first polymers with these bonds and possessed many of the same characteristics as polymers synthesized with S-N bonds. The synthesis and characterization of comb block copolymers with arms composed of poly(lactic acid), poly(butyl acrylate), and poly(styrene-b-vinylpyridine) were described. The self-assembled morphologies in the solid state of comb tri- and tetrablock copolymers with poly(styrene) were also described. These assemblies demonstrated that well-ordered and complex morphologies were assembled from these polymers. The steric effect of substitutions on oxanorbornenes in ring opening metathesis polymerization (ROMP) was investigated. Oxanorbornenes substituted with methyls at the bridgehead positions showed limited reactivity with the Grubbs first and second generation catalysts and the Grubbs first generation methylidene catalyst.

Nowadays, polymer chemists undertake considerable efforts to achieve the preparation of new macromolecules and a perfect control over the macromolecular engineering, i.e. the mass parameters but also over the chain and end-group compositions, topology, etc… is definitively expected. In addition, more complex architectures, such as brush (co)polymers, jellyfish-like topologies…, are required to improve or drastically modify the physicochemical properties of the materials. As a direct consequence of the development of such complex molecular objects, sophisticated techniques are required for the in-depth characterization of the macromolecules, since the exact compositions and structures should be fully and unambiguously identified. Given the fact that the usual characterization tools such as Nuclear Magnetic Resonance (NMR) and Gel Permeation Chromatography (GPC) are extensively used, their abilities have been intensively developed to account for the increasing complexity and diversity of the targeted molecules. Nevertheless, all the usual techniques are averaging methodologies since they only provide pieces of information about the polymer mixture instead of affording data on the individual macromolecules. Since few decades, mass spectrometry (MS) has become as used as NMR and GPC for polymer characterization. In the context of large molecules analysis, MS undoubtedly underwent an impressive craze with the development of two modern ionization procedures, namely Electrospray Ionization (ESI) and Matrix-assisted Laser Desorption/Ionization (MALDI). Those ionization procedures permit the vaporization of macromolecules allowing the intact polymers to be analyzed without a too extensive level of degradation. ESI and MALDI are often considered as soft ionization methods since they offer the possibility to observe ions corresponding to the intact molecules. After their production in the ion source, ions corresponding to the polymer molecules can be mass analyzed by the mass spectrometer and important parameters such as the molecular weight distribution (Mn and Mw), polydispersity index (PDI), the nature of the monomer units and the end-groups can be derived from the measure of the mass-to-charge ratios of the produced ions. In the first part of the present thesis, we studied the MS behavior of different classes of polymers when submitted to ESI and MALDI ionizations. The investigations were devoted to the validation of MS as a truly reliable methodology for fragile polymers such as aliphatic polyesters for instance. In this context, a preliminary MS investigation on semi-telechelic polyethers revealed the importance of the source parameters for the characterization of polymers presenting fragile moieties. We also demonstrated the huge importance of the matrix molecule selection for the MALDI analyses of polymers. In particular, we introduced a new matrix for the MALDI measurements of electroconjugated polymers such as polythiophenes. After the study of the influence of the source parameters on the MS data, a complete study by single stage MS and double stage MS (MS/MS) on newly synthesized polylactides (PLA) was performed. The PLA samples were prepared following original procedures using carbene as catalyst. Finally, to achieve the MS study of PLA ions, we used ion mobility-mass spectrometry (IM-MS) experiments to obtained information on the tridimensional structure of the gas phase PLA ions. In particular, we put a special emphasis on the influence of the charge and size of the polymer chains on their gas-phase conformations. The conclusions derived from the MS/MS and IM-MS results were fully supported by theoretical calculations. In the second part of the thesis, the acquired MS experience was applied to the fine characterization of macromolecules presenting complex architectures obtained by two different polymerization procedures: (i) cobalt-mediated radical polymerization of inter alia acrylonitrile and vinyl acetate and (ii) ring-opening polymerization (ROP) of lactones using non-organometallic catalysts. In particular, mass spectrometry was used to tune the experimental conditions for the ROP of â-lactones using different phosphazenes as catalysts. As an ultimate conclusion, this work points to the very efficient synergy between polymer synthesis, mass spectrometry and theoretical calculations. We believe that this thesis paves the way for innumerable possibilities in the future.

Η παρούσα εργασία αναφέρεται σε νανοσύνθετα βιο-αποικοδομήσιμα οργανικά πολυμερή, με κύρια πολυμερική μήτρα το πολυγαλακτικό οξύ (PLA). Η ερευνητική κοινότητα δείχνει μεγάλο ενδιαφέρον για την χρήση και την ανάπτυξη των βιοδιασπώμενων πολυμερών. Με αυτά αναμένεται να μειωθούν οι επιπτώσεις των πλαστικών υλικών στο περιβάλλον. Στην βιβλιογραφία υπάρχει μεγάλη δραστηριότητα για την ανάλυση του ανθρακικού αποτυπώματος των διασπώμενων πολυμερών. Επίσης, η ερευνητική κοινότητα εστιάζει την προσοχή της και στην μελέτη των ιδιοτήτων των βιοδιασπώμενων πολυμερών. Στο μέλλον αναμένεται να μπορέσουν να χρησιμοποιηθούν σε τομείς που τώρα, λόγω των περιορισμένων μήχανικών τους ιδιοτήτων δεν εφαρμόζονται. Βασικό αντικείμενο μελέτης στην εργασία αυτή ήταν η αλληλεπίδραση οργανικών σφαιρικών νανοσωματιδίων από πολυ(οξικό βινυλεστέρα) με το πολυγαλακτικό οξυ. Για να δημιουργηθεί μια εικόνα της συμπεριφοράς του πολυγαλκατικού οξέος σαν πολυμερική μήτρα, συντέθηκαν και αξιολογήθηκαν μίγματα απο ομοπολυμερή πολυ(οξικού βινυλεστέρα) (PVAc) πολυβινυλικης αλκοόλης (PVOH) και πολυαμιδίου (PA11, PA12). Ύστερα παρασκευάσθηκαν νανοσύνθετα φιλμ απο νανοσωματίδια δικτυωμένου πολυστυρολίου (NPs-PS), δικτυωμένου πολυ(οξικού βινυλεστέρα) (NPs-PVAc) και νανοσωματίδια δικτυωμένης παλυ(βινυλικής αλκοόλης) (με βαθμούς υδρόλυσης H.D.: 100, 50, 48 και 38%). Εν συνεχεία, στην πολυμερική μήτρα απο PLA εισήχθησαν νανοδομές δικτυωμένου πολυ(στυρενοσουλφονικού δεκαέξυλου τριμεθυλαμμωνίου) (PSSAmC16-ΑΝ) σε διάφορες αναλογίες (1, 2, και 5%) και νανοδομημένα δίκτυα δικτυωμένου πολυστυρολίου (PS-NN). Τέλος οι μηχανικές ιδιότητες όλων των φιλμ αξιολογήθηκαν μέσω δοκιμής τάσης-εφελκυσμού και τα μορφολογικά τους χαρακτηριστικά μελετήθηκαν μέσω της ηλεκτρονιακής μικροσκοπίας σάρωσης SEM. / The scientific community shows great interest in the use and development of biodegradable polymers, due to their low impact on the environment. In literature there is plenty of research activity on the analysis of biodegradable polymers in comparison to the CO2 emission during the life cycle of polymer products. The carbon footprint of biodegradable polymers is far smaller than those of conventional polymers. The biodegradable materials are so desirable because these are expected to overcome significant problems such as environmental pollution, waste management issues which are created by plastics, as well as their oil dependence. Thus, the research community is focused on the study of the properties of biodegradable polymers and their potential use in applications where their design is mainly limited by the material's mechanical properties, such as modulus, strength and other characteristic properties of the behavior of the polymers (such as miscibility, optical transparency and barrier properties). In the present work blends of PLA with the homopolymers polystyrene (PS), polyvinyl acetate (PVAc) and polyamides (PA11, PA12) were made and the quality of the synthesized films was assessed. In a further step, spherical organic nanoparticles of PS, PVAc (either non-hydrolyzed or hydrolyzed with hydrolysis degree H.D.: 100, 50, 48 and 38%) as well as assymetric nanostructures of polystyrene sulfonate ammonium salt (PSSAmC16-AN) and PS-NN were incorporated into the PLA matrix in various percentages (1, 2, and 5%). Afterwards the mecahanical properties of the blends were evaluated by stress-strain measurements, whereas their morphological characteristics were tested through scanning electron microscopy (SEM).

The primary objective of my thesis was to investigate the effect of crimp-like fibrous scaffolds on bovine fibroblasts and to develop a scaffold for anterior cruciate ligament (ACL) tissue engineering. To achieve this objective, fibrous biodegradable polymeric scaffolds were fabricated, which upon relaxation developed a crimp-like structure, which resembled the crimp seen in native collagen. The understanding of the crimp mechanism allowed for controlling crimp-like patterns in various polymer fibre systems, and was determined to be due to residual stress coupled with an operating temperature (Top) above the glass transition temperature of the polymer (Tg). The benefit of crimp was evaluated by seeding fibroblasts on crimp-like fibres that were subjected to dynamic mechanical loading. The results showed a significant increase in extracellular matrix (ECM) accumulation by fibroblasts that experienced crimp unfolding. In addition, fibroblasts seeded on mechanically stimulated crimp-like fibrous scaffolds formed ECM bundles that resembled collagen fibre fascicles. Two separate studies were conducted to fabricate fibrous scaffolds with high modulus: one on thermoplastic polyesters and the other on a photocrosslinkable polyester. Of the thermoplastic polyesters investigated, poly(L-lactide-co-D,L-lactide) P(LLA-DLLA) exhibited the highest modulus, and was the most resistant to hydrolytic degradation. These fibres were placed in a heated aqueous environment to exhibit a crimp-like pattern similar to that of native collagen. Bovine fibroblasts were shown to attach, proliferate and deposit ECM on the surface of the P(LLA-DLLA) fibrous scaffolds. In addition, the deposited ECM appeared to be organized in distinctive bundles that resembled fascicles found in native ACL. However, upon crimp unfolding the crimp was not completely recovered. Photocrosslinkable poly(L-lactide-co-trimethylene carbonate cinnamate) P(LLA-TMC cinnamate) fibres in addition to supporting cell proliferation and ECM accumulation, completely recovered their crimp-like pattern, via [2 + 2] cycloaddition of the cinnamate groups. The recovery of crimp upon unfolding is a novel design feature incorporated into electrospun fibres as it innately mimics the function of collagen fibres found in the ACL. From the results obtained it is evident that crimp and its unfolding are key design features/conditioning techniques that need to be incorporated into fibrous scaffolds that possess high modulus, intended for ligament tissue engineering. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2012-01-05 14:11:25.965

Charles University in Prague, Faculty of Pharmacy in Hradec Králové Department of: Pharmaceutical technology Consultant: PharmDr. Ondřej Holas, Ph.D. Student: Silvia Bacskaiová Title of Thesis: Biodegradable polymeric nanoparticles preparation The present scientific progress in an important rate conduces to nanomedicine development, which aims to reengineering of cancer pharmacotherapy and other substantial diseases. The main intention of this graduation thesis is the study of surface-active chemical's effects on the final properties of nanoparticles. The theoretical part is focused on the nanoparticles likedrugs vehicles, synthesis of biodegradable nanoparticles, themselves applications in the cancer therapy, diseases accompanied by inflammations, vaccination and for another different purposes. The theoretical part also contents characterization of active and passive goal- directed distribution by diseases, microencapsulations, synthesis of nanoparticles by polymerization and from previously synthesized polymers and definition of physical- chemical properties of nanoparticles. The experimental part is more extensive and concerned with the optimalization of reaction conditions of nanoparticles synthesis, with selection of advisable concentracion and type of surfactant. In the experimental part were...