During this project, photocatalytic material, nano sized titanium dioxide, was introduced into poly (lactic acid) to produce functional surface capable of self-cleaning property. Samples containing 0%, 5%, 10%, 15% and 20% titanium dioxide were prepared and etched with proteinase K to expose the nano particles on the surface. It was shown that the nano titanium dioxide could dispersed in the polymer matrix pretty well, it was also found that the nano particles affected the thermal and mechanical properties of the polymer matrix differently , due to difference in concentrations of nano filler. The self-cleaning property was evaluated by decolouration of stains caused by coffee and red wine, also by detecting degradation of methylene blue via a UV-vis spectrophotometer. By measuring changes in absorbance of light at 664nm wavelength after a maximum of 24h UV irradiation, it was possible to measure the degradation property of the samples. / Program: Masterutbildning i textilteknik

<div>Wounds are created in soft and hard tissue through surgery or disease. As the wound heals, the tissue is held in place using sutures or staples for soft tissue or plates, pins, or screws for hard tissues. These fixation methods inherently damage the surrounding healthy tissue. Surgical adhesives are a non-damaging alternative to these methods. In order to be effective, surgical adhesives must be biocompatible,</div><div>adhere strongly in a moist environment, and have mechanical properties similar to those of the native tissue.</div><div><br></div><div><div>To address the design criteria for surgical adhesives, we look to nature to find inspiration from compounds that provide these properties. Mussels use catechol-based</div><div>molecules to adhere to surfaces in wet and turbulent environments. Incorporating catechols into polymer systems can provide adhesion even in moist biological environments.</div><div>Mimics of elastomeric proteins from soft tissue can be used as backbones for soft and flexible adhesive systems. In particular, elastin-inspired proteins have a well-defined modular sequence that allows for a range of design choices. In this work, we explored the behavior of elastin- and mussel-inspired natural and synthetic polymers in biologically relevant environments.</div></div><div><br></div><div><div>First, the cytocompatibility of a catechol-containing poly(lactic acid) (cPLA) hard tissue adhesive was studied. The cPLA polymer was reacted with iron- or periodatebased</div><div>crosslinkers and compared to PLA. Fibroblasts grown directly on cPLA or cultured with leachate from cPLA had high viability but slower growth than cells on PLA. The periodate crosslinker was significantly cytotoxic, and cells grown on cPLA crosslinked with periodate had reduced metabolism and slowed growth. Cells grown on or in leachate from iron-crosslinked cPLA had similar viability, metabolism, and growth to cells on or in leachate from cPLA. The iron-crosslinked cPLA is a promising</div><div>cytocompatible adhesive for hard tissue applications.</div></div><div><br></div><div><div>Second, two elastin-like proteins (ELP) were developed that had pH-sensitive properties in solution and when crosslinked into hydrogels. Both ELPs had a large number of ionizable tyrosine and lysine residues, and one design also had a large number of ionizable histidine and aspartic acid residues. The stiffness of the hydrogels was maximized at pH values near the isoelectric point of the protein. The stoichometric ratio of crosslinker used affected hydrogel stiffness but did not significantly alter the pH-sensitivity of the gel. The crosslinked gel shrank when swelled at physiological pH. The pH-sensitive mechanical properties of hydrogels made from the two ELPs did not vary significantly. The tyrosine and lysine residues in one ELP were also</div><div>chemically blocked through acetylation to lower the isolectric point of the protein. The acetylated hydrogels had maximum stiffness at a pH near the isoelectric point of the acetylated ELP. The stiffness of both the native and acetylated gels were within the range of soft tissue. Through a combination of crosslinker ratio and chemical modification, the pH-responsive properties of the elastin-inspired hydrogels could be tuned.</div></div><div><br></div><div><div>Finally, adhesive proteins were created that were inspired by both elastin and mussels. An ELP was modified to include catechol groups (mELP). The ELP and mELP were optimized for adhesive use in a soft tissue system. A warm and humid environment was used to study the adhesion of these proteins on pig skin. Iron and (hydroxymethyl) phosphine crosslinkers increased the adhesive strength of both proteins, and periodate increased the adhesive strength of mELP. The adhesive strengths of the proteins were maximized when mELP was mixed with iron or when either protein were mixed with (hydroxymethyl)phosphine crosslinkers. These maximized adhesives were 12-17 times stronger than a commercially available sealant. In addition,</div><div>the iron and mELP adhesive formulation achieved high adhesive strengths even when cured for only ten minutes. This adhesive formula shows promise for adhesive</div><div>applications on soft tissue.</div></div>

Submitted by Maria Aparecida (cidazen@gmail.com) on 2017-04-27T14:21:14Z No. of bitstreams: 1 Ruy Guilherme.pdf: 4333694 bytes, checksum: dc411f45b9fe05154bdee07704d50d65 (MD5) / Made available in DSpace on 2017-04-27T14:21:14Z (GMT). No. of bitstreams: 1 Ruy Guilherme.pdf: 4333694 bytes, checksum: dc411f45b9fe05154bdee07704d50d65 (MD5) Previous issue date: 2017-01-23 / The recent emergence of Free-to-Play games, also known as Freemium games, has considerably changed the way games are made. The definition of monetization strategies is now part of the process of making games. Choosing which strategy to adopt among the various ones and understanding how they work could be an arduous task. When analysing the market, to realize that popular games use similar strategies is not difficult, which demonstrates that the reuse of strategies is common among developers. Although there are catalogs of popular monetization strategies used by Free-to-Play games in the literature, little attention has been given to formalize the description of those strategies, leaving openings for misunderstandings and making the reuse harder. For that reason, a meta-model of Free-to-Play games monetization that allows the representation of Free-toPlay games monetization strategies based on a set of popular strategies is proposed. That meta-model, called Meta-F2P, was elaborated from the investigation of the most rentable Free-to-Play games for mobile devices. Besides that, case studies were used to validate and refine the accuracy, expressiveness and extensibility of that meta-model. Based on the results obtained, the applicability of the meta-model in the process of making games and the advantages and disadvantages of the use of case studies in the concept of meta-models are analyzed. / A recente ascensão dos jogos Free-to-Play, também conhecidos como Freemium, provocou mudanças consideráveis na forma como os jogos são produzidos. A elaboração de estratégias de monetização passou a fazer parte do processo de desenvolvimento. Escolher qual estratégias adotar dentre as diversas existentes e entender o seu funcionamento pode tornar esta uma tarefa árdua. Ao se analisar o mercado não é difícil perceber que os jogos mais rentáveis abordam estratégias de monetização similares, demonstrando que reuso de estratégias é uma abordagem adotada por diversos desenvolvedores. Embora existam na literatura catálogos de estratégias de monetização populares em jogos Free-to-Play, pouca atenção tem sido dada no intuito de formalizar a descrição das estratégias, dando margem para interpretações errôneas e dificultando o reuso. Assim propõe-se um meta-modelo que permite representar as estratégias de monetização de jogos Free-to-Play a partir de um conjunto de estratégias populares. O meta-modelo denominado Meta-F2P foi elaborado a partir da análise de jogos Free-to-Play para dispositivos móveis mais rentáveis. Além disso, utilizou-se estudos de caso para a validação e o refinamento da exatidão, expressividade e extensibilidade do meta-modelo. A partir dos resultados obtidos analisa-se a aplicabilidade do meta-modelo no processo de design de jogos e as vantagens e desvantagens da aplicação de estudos de caso na elaboração de meta-modelos.

Tese de Mestrado Integrado. Engenharia Mecânica. Faculdade de Engenharia. Universidade do Porto. 2012

L’objectif de ce travail est de préparer des polymères composites antimicrobiens, utilisant de l’acide polylactique (PLA) et/ou du caoutchouc naturel époxydé et incluant des particules d’argent insérées dans des matrices zéolites (AgZ), agissant en tant que composé actif. Un des verrous contrôlant l’activité antibactérienne des matériaux synthétisés est relié à l’étude de l’absorption de l’eau. En effet la mise en œuvre de composites PLA antibactériens rencontre le problème du caractère faiblement hydrophile de PLA, induisant une faible efficacité antimicrobienne. Ainsi afin d’amplifier l’activité antibactérienne des composites AgZ/PLA, une solution prometteuse consiste à introduire un second polymère hautement polaire et flexible. Le caoutchouc naturel époxydé a été ainsi sélectionné pour être associé au composite AgZ/PLA et le taux d’absorption d’eau mesuré témoigne d’un accroissement notable. La morphologie et la distribution des particules AgZ a été étudiée. L’accroissement remarquable du caractère antibactérien des composites ENR/AgZ/PLA a été démontré ; ainsi des tests menés sur S. aureus montrent que la croissance bactérienne a été inhibée à hauteur de 98-99%. L’étude a aussi été menée en fonction de la proportion de caoutchouc et des particules AgZ. De plus les composites ENR/AgZ/PLA possèdent une plus haute résistance à l’impact comparés à l’emploi de PLA pur, suggérant ainsi que ces nouveaux composites pourront constituer des matériaux de choix pour des applications à la fois antibactériennes et nécessitant une résistance à l’impact forte. / The aim of this work is to prepare antibacterial polymers composites, involving especially poly(lactic acid) (PLA) and epoxidized natural rubber (ENR) in the presence of silver-substituted zeolites (AgZ) as an active ingredient. Herein, the key to control the antibacterial activity of the composites which is the water absorption characteristic was thoroughly studied. In general, the fabrication of antibacterial PLA composites encounters with the problem relating to the poor hydrophilicity of PLA which is the cause of antibacterial ineffectiveness. To enhance the antibacterial activity of the composites, blending with the second polymer having high polarity and flexibility is a promising way to produce the antibacterial AgZ/PLA composite. Herein, epoxidized natural rubber (ENR) was selected to blend with AgZ/PLA composites and the increase in the water absorption percentage could be observed. The morphology as well as the AgZ distribution in the composites were also investigated. The remarkable enhancement of antibacterial activity of ENR/AgZ/PLA composites was observed because more than 98-99% inhibition of S. aureus growth was found. Furthermore, the effects of rubber content and amount of AgZ on the antibacterial activity of the composites were investigated. Moreover, the ENR/AgZ/PLA composites possessed the higher impact resistance compared to neat PLA, suggesting that the improved composites might be a choice in applications at which both antibacterial activity and impact resistance property are of great importance.

La substitution des matériaux composites à base de polymères d'origine fossile renforcés de fibres minérales ou synthétiques, par des bio-matériaux conçus par association de bio-polymères et de renforts fibreux végétaux, permet d'envisager un recyclage et/ou une bio-dégradation en fin de vie. Dans cet objectif, nous avons élaboré un bio-composite à base de bois et de bio-polymère d'acide lactique, par imprégnation vide / pression d'acide lactique oligomérisé, contenant ou non un catalyseur chimique de polymérisation, dans les cellules de bois, suivie d'un chauffage en étuve. L'objectif de ce travail était de provoquer la polymérisation des oligomères d'acide lactique in-situ, et d'induire éventuellement un greffage de ces molécules sur les sites hydroxyles libres du bois, dans le but d'améliorer les propriétés du matériau. Nous avons démontré une polymérisation in-situ effective, et une forte interaction entre le bois et les chaînes d'acide lactique, toutefois non greffées. L'action du bio-polymère sur la structure lignocellulosique est également mise en évidence par un « ramollissement » important du bois, apparaissant à un stade intermédiaire de l'étape de chauffage, vraisemblablement dû à une réaction entre les oligomères d'acide lactique et la lignine contenue principalement dans la lamelle mitoyenne. Une forte coloration traduit d'autre part une probable réaction entre les catalyseurs chimiques et la cellulose. Le cycle de chauffage achevé, le matériau se trouve dans un état final rigide dont les performances ont été étudiées. Il s'avère que le traitement confère une excellente stabilité dimensionnelle au bois : environ 70% d'efficacité anti-gonflement. Une amélioration de la résistance à l'attaque fongique a été observée. En ce qui concerne les propriétés mécaniques, les résistances à la flexion et la compression sont peu influencées, alors que l'on note une forte augmentation de la dureté de surface, et une diminution de la résistance au cisaillement, due à la fragilisation de la lamelle mitoyenne. Ainsi, les densité et dureté élevées, ainsi que la stabilité du matériau laissent envisager des applications dans certains domaines industriels comme la parqueterie. Dans l'état intermédiaire « ramolli », des applications de mise en forme, telles que le matriçage ou le cintrage sont également concevables.

Bien que les techniques d'autotest intégré soient en perpétuel développement sous forme de théories et de schémas de conception, leur réalisation concrète et leur implémentation posent des problèmes cruciaux. Une stratégie d'autotest intégré est proposée dans cette thèse pour des circuits générés par compilation de silicium. Le schéma UBIST d'unification du test en-ligne et hors-ligne assure la plupart des tests nécessaires durant la vie d'un circuit intégré (test de fin de fabrication, test de maintenance, test en-ligne,...). A la base du schéma ubist se trouve le schéma self-checking (test en-ligne, pour lequel le circuit est compose de blocs fonctionnels strongly fault secure (sfs) et de contrôleurs strongly code disjoint (scd). Le but a atteindre par de tels circuits est couramment appelé le totally self-checking goal, qui consiste a détecter la première erreur survenant aux sorties du bloc fonctionnel, sous forme d'indication d'erreur sur les sorties du contrôleur. Autour de ce schéma self-checking est implémentée une structure de test, du type bilbo, assurant des phases de test hors-ligne, qui a pour objectif d'augmenter le taux de couverture des pannes multiples et de renforcer les propriétés SFS et SCD pour certains blocs fonctionnels et contrôleurs. L'unification des tests en-ligne et hors-ligne permet de tirer les avantages de chacun de ces tests, permettant une implémentation efficace d'autotest intégré. Une méthodologie de conception pour implémenter ce schéma UBIST est proposée pour des parties contrôle hiérarchiques a base de plas et des parties operatives parallèles en structure bit-slice (du type de celle du mc 68000). Ce sont les architectures cibles utilisées par le compilateur de silicium SYCO (développé au sein de l'équipe d'architecture des ordinateurs du laboratoire TIM3/IMAG). Une solution topologique efficace est proposée pour ces schémas UBIST

Recherche de nouvelles méthodes de synthèse logique sur différentes cibles technologiques: PLA détaillé libre et PLD de type PAL. Une méthode originale de minimisation deux couches d'un ensemble de fonctions booléennes sur une cible de type PLA libre est étudiée. Une méthode de synthèse sur les réseaux programmables de type PAL, dont les dimensions et les structures sont figées, est aussi proposée

Fundamental to all biological processes is the interplay between biomolecules such as proteins and nucleic acids. Studies of interactions should therefore be more informative than mere detection of expressed proteins. Preferably, such studies should be performed in material that is as biologically and clinically relevant as possible, i.e. in primary cells and tissues. In addition, to be able to take into account the heterogeneity of such samples, the analyses should be performed in situ to retain information on the sub-cellular localization where the interactions occur, enabling determination of the activity status of individual cells and allowing discrimination between e.g. tumor cells and surrounding stroma. This requires assays with an utmost level of sensitivity and selectivity. Taking these issues into consideration, the in situ proximity-ligation assay (in situ PLA) was developed, providing localized detection of proteins, protein-protein interactions and post-translational modifications in fixed cells and tissues. The high sensitivity and selectivity afforded by the assay's requirement for dual target recognition in combination with powerful signal amplification enables visualization of single protein molecules in intact single cells and tissue sections. To further increase the usefulness and application of in situ PLA, the assay was adapted to high content analysis techniques such as flow cytometry and high content screening. The use of in situ PLA in flow cytometry offers the possibility for high-throughput analysis of cells in solution with the unique characteristics offered by the assay. For high content screening, it was demonstrated that in situ PLA can enable cell-based drug screening of compounds affecting post-translational modifications and protein-protein interactions in primary cells, offering superior abilities over current assays. The methods presented in this thesis provide powerful new tools to study proteins in genetically unmodified cells and tissues, and should offer exciting new possibilities for molecular biology, diagnostics and drug discovery. 

We studied PLA-microcrystalline cellulose composites, focusing on the effects of processing, particle size and surface modification. The thermal and mechanical properties of these PLA based composites were studied and the effect of cellulose addition on PLA degradation was analyzed. For our system, the degradation rate was found to depend on initial sample crystallinity, pH of the degradation media and cellulose content of the composite. Composites were prepared using solution processing and melt mixing methods. The processing methods influenced the polymer's ability to crystallize affecting the mechanical properties. Isothermal crystallization studies carried out to study the kinetics of crystallization showed melt processed samples to have lower half time for crystallization and higher value for the Avrami exponent. The crystallization rate of PLA was also found to depend on surface chemical composition of cellulose particles and the particle size. Influence of filler surface modification on the composite properties was studied via grafting of lactic acid and polylactic acid to cellulose particles and the effect of filler size was studied using hydrolyzed microcrystalline cellulose particles. A simple esterification reaction that required no external catalyst was used for surface modification of cellulose particles. Surface modification of cellulose particles enhanced the static and dynamic mechanical properties of the composite samples due to improvement in the PLA-cellulose compatibility that resulted in better interfacial interactions. The utility of cellulose, available from a renewable resource, as an effective reinforcement for PLA is demonstrated.