Les travaux de recherche présentés ici avaient pour objectif principal la synthèse de copolymères statistiques à base d’éthylène et d’acide acrylique (AA). Pour cela, la déprotection des groupements esters d’un copolymère statistique précurseur, le poly(éthylène-co-(tert-butyl)acrylate), a été effectuée par hydrolyse à l’aide d’iodure de triméthylsilyle. La synthèse de ce précurseur est réalisée par polymérisation catalytique en présence d’un système à base de Palladium (Pd). Le deuxième objectif a été d’étudier et de caractériser des polymères synthétisés à l’état solide et en suspension colloïdale. Plusieurs copolymères précurseurs comprenant différents pourcentages molaires en tert-butyl acrylate (4 à 12% molaires) ont été synthétisés avec succès, puis déprotégés par hydrolyse pour obtenir des poly(éthylène-coacide acrylique) (pE-co-AA) avec différentes compositions. Seuls les copolymères comprenant 10% molaire ou plus de AA sont solubles dans le Tétrahydrofurane (THF) et uniquement dans ce solvant. De telles solutions peuvent être dialysées dans l’eau, ce qui conduit à un échange lent entre cette dernière et le THF, et l’autoassemblage du copolymère dans l’eau peut ensuite être étudié. C’est ainsi qu’ont pu être observées des nanoparticules stables dans le temps dont le comportement est sensible au pH et à la température. Les polymères synthétisés ont été caractérisés par Résonance Magnétique Nucléaire (RMN) ainsi que par spectroscopie Infra-Rouge (IR), avant et après déprotection. Les pourcentages molaires d’AA ont été déterminés par combinaison des résultats de RMN et ii de titrages conductimètriques. A l’état solide, les échantillons ont été analysés par Calorimétrie différentielle à balayage (DSC) et par Diffraction des rayons X. Les solutions colloïdales des polymères pE-co-AA ont été caractérisées par Diffusion dynamique de la lumière et par la DSC-haute sensibilité. De la microscopie électronique à transmission (TEM) a permis de visualiser la forme et la taille des nanoparticules. / The first objective of this research is to synthesize random linear copolymers of ethylene and acrylic acid (AA). The synthesis relies on the deprotection of the functional groups in the copolymer’s precursor, which is represented by poly(ethylene-co-tertbutyl acrylate). The synthesis of the precursor was realized by the catalytic approach, where Pd-based catalytic systems are frequently utilized nowadays. The deprotection was carried out by hydrolysis of the ester functionality using trimethylsilyl iodide agent. The second objective is to investigate and characterize the synthesized polymers in the bulk and in colloidal solution. A set of different precursor polymers with various degrees of molar incorporation of tertbutyl acrylate (from 4 to 12 mol %) was successfully synthesized and deprotected. The resulting poly(ethylene-co-acrylic acid) copolymers were found to be soluble in tetrahydrofuran THF, when the molar incorporation of AA reaches the value of 12 and more. This aspect gave the possibility to study the self-assembly of this copolymer in aqueous medium by slow THF to water exchange (dialysis). It was found that the copolymers self-assemble into nano-sized structures and these nanoparticles remain stable in colloidal solution for extended periods of time. Moreover, it was shown that the nanoparticles formed by the discussed copolymer possess thermo- and pH-responsive behaviour. The polymers synthesized were characterized by nuclear magnetic resonance (NMR) and infrared spectroscopies (IR) before and after deprotection. The bulk samples were analyzed by conventional differential scanning calorimetry and by X-ray diffraction iv technique. The molar percentages of AA were determined using a combination of NMR and conductimetric titration. Colloidal solutions of pE-co-AA copolymers were analyzed by dynamic light scattering and high-sensitivity differential scanning calorimetry techniques. The nanoparticles formed were visualized and characterized by transmission electron microscopy.

This thesis explores ideas of everydayness, the mundane, and the repetitive emptiness of consumer culture. It looks at the malaise that plagues everyday life and examines several attempts throughout history to break from its grips which revolve around a search for a more ideal state. This research includes utopias of modernism, the transcendental, the communal living of Shakers and Early Christians, ascetic monks and The Desert Fathers. These ideas have shaped my studio practice as I construct installations based on worlds which allude to the eternal, the otherworldly, and the fragility of our physical world when compared to more eternal spiritual archetypes.

Ce travail de thèse décrit la synthèse de copolymères diblocs amphiphiles par polymérisation radicalaire contrôlée par transfert d'iode en mode inverse (RITP). Dans un premier temps, des homopolymères à base de monomères activés (styrène, acrylate de méthyle, méthacrylate de méthyle), non activés (acétate de vinyle) et fonctionnels (chlorométhylstyrène, acrylate de tert-butyle), ont été synthétisés par RITP. Des aspects tels que le contrôle des masses molaires ainsi que la fonctionnalité en iode du bout de chaîne ont été examinés. Afin de démontrer la compatibilité de la RITP avec d'autres techniques de polymérisation contrôlée/vivante (non radicalaires), le copolymère amphiphile non-ionique poly(styrène)-b-poly(2-méthyl-2-oxazoline) (PS-b-P(MOx)) a été élaboré par la voie toute iode en procédé « one-pot » en combinant de manière consécutive la RITP du styrène avec la polymérisation cationique par ouverture de cycle (CROP) de la 2-méthyl-2-oxazoline. Par ailleurs, des copolymères cationiques poly(styrène)-b-poly(chlorométhylstyrène) quaternisé avec la triéthylamine (PS-b-PCMS+) et anioniques poly(styrène)-b-poly(acide acrylique) (PS-b-PAA-) ont été synthétisés par RITP du styrène suivie de l'ITP du bloc hydrophile. Tous ces copolymères amphiphiles ont été obtenus à partir de polystyrène iodé (PS-I) de faibles masses molaires, allant de 1000 à 3000 g.mol-1, jouant le rôle de macro-amorceurs (CROP) ou de macro-agents de transfert (ITP). L'étude de l'auto-organisation en phase aqueuse de ces copolymères amphiphiles a révélé la formation de micelles pour des concentrations supérieures à la concentration d'agrégation critique (CAC) dont la valeur a été déterminée par diffusion dynamique de la lumière (DDL) et spectroscopie de fluorescence. Enfin, des résultats très prometteurs ont été obtenus dans l'utilisation d'un copolymère cationique amphiphile PS-b-PCMS+ comme agents structurants de matériaux siliciques mésoporeux nanostructurés élaborés par procédé sol-gel en milieu basique. La synthèse de ces copolymères amphiphiles ainsi que leur caractérisation physico-chimique ont mis en exergue que la RITP permet de couvrir la synthèse de différentes catégories de copolymères amphiphiles, tout en étant une technique simple à mettre en œuvre, peu couteuse et robuste. / This manuscript describes the synthesis of amphiphilic diblock copolymers by reverse iodine transfer polymerization (RITP). Firstly, homopolymers derived from activated (styrene, methyl acrylate, methyl methacrylate), non-activated (vinyl acetate) and functional monomers (chloromethylstyrene, tert-butyl acrylate) synthesized by RITP, were studied. Aspects including molecular weight control as well as iodine chain-end functionality were investigated. In order to highlight the compatibility of RITP with other living/controlled (non-radical) polymerization techniques, a poly(styrene)-b-poly(2-methyl-2-oxazoline) (PS-b-P(MOx)) non-ionic copolymer was conceived through an ‘all-iodine', ‘one-pot' process by combining successively RITP of styrene with cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline. Besides, poly(styrene)-b-poly(chloromethylstyrene) quaternized with triethylamine (PS-b-PCMS+) cationic copolymers and poly(styrene)-b-poly(acrylic acid) (PS-b-PAA-) anionic copolymers were elaborated by RITP of styrene, followed by ITP of the hydrophilic moiety. All these amphiphilic copolymers were obtained from iodine-bearing chain-end poly(styrene) (PS-I) of low molecular weights, in the range of values of 1000 to 3000 g.mol-1, playing the role of macro-initiators (CROP) or macro-transfer agents (ITP). Studies of the self-assembly of these amphiphilic copolymers in aqueous phases revealed the formation of micelles for concentrations superior to the critical aggregation concentration (CAC). The latter value was determined by dynamic light scattering (DLS) and fluorescence spectroscopy. Moreover, highly-promising results were obtained in the use of PS-b-PCMS+ cationic copolymers as structuring agents meant for the elaboration of nanostructured, mesoporous silica-based materials through the sol-gel process in basic medium. Both the synthesis of the amphiphilic copolymers and their physico-chemical characterizations have evidenced that RITP fosters the synthesis of different categories of amphiphilic copolymers, while being a simple, cheap and robust technique.

Les objectifs du travail présenté ici sont de comprendre les procédés de formulation des gouttelettes et des particules afin de faire des hybrides polymère-polymère de qualité en dispersions aqueuses et d’utiliser notre compréhension fondamentale de ces procédés pour : 1. Augmenter le taux de conversion de(s) monomère(s) autant que possible. 2. Comprendre l’impact de ces procédés sur les propriétés des films hybrides. Des cas particuliers ont été étudiés dans des conditions commercialement viables (taux de solide de 50% en masse) basés sur deux systèmes appelés alkyde-acryliques et polyuréthane-acrylique. La préparation des miniémulsions, la polymérisation en miniémulsion et la caractérisation des latex hybrides, l’incorporation chimique d’alkyde et de polyuréthane dans les monomères acryliques ont été étudiés en détails. Nous sommes parvenus à synthétiser et caractériser des latex hybrides avec de haut taux de solides (50% en masse) composés de particules de 100nm de diamètre utilisables dans des applications de revêtement et d’adhésifs / The objectives of work presented in this thesis are to understand droplet and particle formulation processes in order to make useful polymer-polymer hybrids in aqueous dispersions and use our fundamental understanding of these processes to: 1. Improve monomer conversion as much as possible. 2. Understand impact of these processes on hybrid film properties. Specific case studies of interest under commercially feasible conditions (i.e. solids content of 50wt %) were done based on two systems namely alkyd-acrylic and polyurethane-acrylic. Miniemulsification, miniemulsion polymerisation and characterisation of hybrid latex, chemical incorporation of alkyd and polyurethane to acrylic monomers were studied in detail. We have been able to successfully synthesise and characterise hybrid latex of about 100nm in particle diameter and high solids content (50wt %) to be used in coating and adhesive applications

O objetivo deste trabalho foi avaliar, por meio de estudo in vitro, o efeito de soluções químicas de higienização quanto à ação antimicrobiana e os efeitos sobre as propriedades da resina acrílica termicamente ativada. Para a ação antimicrobiana, corpos de prova circulares (15mm x 3mm) foram esterilizados por radiação em forno micro-ondas e contaminados com suspensão de 106 UFC/mL dos microrganismos: Candida albicans, Candida glabrata e Streptococcus mutans e incubados a 37ºC por 48hs. Em seguida, os espécimes foram imersos nas seguintes soluções: Grupo I - PBS (controle); Grupo II - Solução à base de Ricinus communis a 6,25%; Grupo III - Hipoclorito de sódio 0,20%; durante 20 minutos, e, Grupo IV - Peróxido Alcalino Efferdent® Power Clean Crystals, durante 3 minutos, e lavadas (PBS) e imersas em meio Letheen. A suspensão resultante foi diluída (100 e 10-3) em solução salina estéril e alíquotas foram semeadas em meio específico. Após incubação (37ºC por 24hs), as colônias foram contadas para o cálculo de UFC/mL. Para análise das propriedades da resina acrílica, corpos de prova circulares (15mm x 3 mm) e retangulares (65mm x 10mm x 3,3 mm) foram imersos nas soluções, simulando 05 anos de imersões curtas. Antes e após as imersões, foram submetidos a análise de cor (Colorímetro Color Guide 45/0) e NBS (NBS=&Delta;E* x 0,92); de dureza Knoop (microdurômetro Microhardness Tester Shimadzu); de rugosidade de superfície (rugosímetro Surftest SJ - 201P, Mitutoyo Corporation; microscópio confocal a laser 3D Olympus LEXT OLS4000®, Japão); de morfologia de superfície (microscópio eletrônico de varredura EVO 10 - MEV, Carl Zeiss Microscopy GmbH, Jena, Alemanha); e de resistência à flexão (Máquina Universal de Ensaios DL 2000, EMIC). Os dados com distribuição normal foram analisados por ANOVA, seguido pelo teste de Tukey; os dados com distribuição não-normal, foram analisados pelos testes de Kruskal-Wallis e Dunn (&alpha;=0,05). Os resultados mostraram que o hipoclorito reduziu a zero a contagem de UFC dos três micro-organismos, os grupos do Ricinus communis e do peróxido Efferdent tiveram ação moderada frente Candida glabrata (p<0,001) e S. mutans (p=0,001), respectivamente. Quanto as propriedades da resina, a solução de Ricinus communis causou leve alteração de cor (p=0,030), segundo NBS; maiores alterações de dureza (p<0,001), rugosidade superficial em rugosímetro (p=0,006) e microscópio 3D (p=0,040) e da resistência à flexão (p<0,001). A maior alteração da morfologia de superfície (MEV) foi observada no grupo do peróxido Efferdent. Pode-se concluir que a solução de hipoclorito de sódio a 0,20% foi a mais efetiva, uma vez que apresentou ação antimicrobiana frente aos três micro-organismos avaliados; as soluções de Candida glabrata e Streptococcus mutans, respectivamente. Quanto à análise das propriedades da resina acrílica, nenhuma das soluções causou alteração clinicamente significante nas propriedades avaliadas / The purpose of this in vitro study was to evaluate the antimicrobial action and adverse effects of denture cleansers on a heat-polymerized acrylic resin. The antimicrobial action was evaluated by samples fabricated on a metallic circular matrix (15mm x 3mm), which were sterilized by microwave (650W, for 6 minutes) and inoculated with a 106 CFU/ml of microorganisms´suspension: Candida albicans, Candida glabrata, and Streptococcus mutans. After contamination, the specimens were incubated at 37ºC for 48hs and then immersed on the following solutions: Group I - Saline (control); Group II - Ricinus communis 6.25% solution based; Group III - Sodium hypochlorite 0.2%; Group IV - Alkaline Peroxide Efferdent® Power Clean Crystals. The samples were then washed (PBS) and immersed in the Letheen medium. The resulting solution was diluted (100 and 10-3) in sterile saline, and aliquots were cultured in the specific medium. After incubation (37ºC for 24hs), according to with characteristic morphology, the number of colonies was measured and the number of CFU / mL calculated. For the adverse effects, circular (15 x 3 mm) and rectangular (65 x 10 x 3.3 mm) test specimens of heat-polymerized acrylic resin were immersed in the solutions, simulating 05 years of short immersions per sanitation period. Before and after the immersions, the samples were evaluated for color alteration (Color Guide Color Guide 45/0) and correlation of the data according to NBS units (NBS = &Delta;E * x 0,92); Knoop hardness (Microhardness Microhardness Tester Shimadzu). Analysis of surface roughness (Surftest SJ-201P rugosimeter, Mitutoyo Corporation; Olympus LEXT OLS4000® 3D laser confocal microscope, Japan), surface morphology (scanning electron microscope EVO 10 - MEV, Carl Zeiss Microscopy GmbH, Jena, Germany); and flexural strength (Universal Testing Machine DL 2000, EMIC) was done. The data that presented normal distribution were analyzed by ANOVA and post-hoc Tukey test; Data that presented non-normal distribution were analyzed by the Kruskal-Wallis and Dunn test (&alpha;= 0.05). The results showed that hypochlorite reduced the CFU of the three microorganisms to zero, the solution of Ricinus communis and Efferdent peroxide had an average action against Candida glabrata (p <0.001) and Streptococcus mutans (p = 0.001), respectively. The solution of Ricinus communis showed color changes (p = 0.030), classified as &ldquo;light&rdquo; according to NBS; (p <0.001), and higher values of surface roughness, when analyzed by the rugosimeter (p = 0.006) and 3D microscope (p = 0.040), and flexural strength (p <0.001). The major change in surface morphology (SEM) was found in the Efferdent peroxide group. It can be concluded that the 0.20% sodium hypochlorite solution was the most effective denture cleanser since it presented antimicrobial action against the three micro-organisms evaluated Candida albicans, Candida glabrata, and Streptococcus mutans, and did not cause clinically significant changes on the heat-polymerized acrylic resin

Este estudo propôs diferentes métodos de incorporação do vanadato de prata nanoestruturado (AgVO3) em uma resina acrílica e avaliou o padrão de incorporação promovido, a capacidade antimicrobiana, o desempenho mecânico, a taxa de liberação de íons prata (Ag) e vanádio (V) e a citotoxicidade. O AgVO3 foi incorporado nas frações de 0-5%, por meio de duas metodologias, (I) Espatulação a Vácuo e (II) Técnica do Filme Polimérico. A caracterização dos espécimes foi realizada por Microscopia eletrônica de varredura e microanálise (MEV/EDS) e Difração de raios X (DRX). A capacidade antimicrobiana foi avaliada por pirosequenciamento genético e o desempenho mecânico por ensaios de resistência à flexão e ao impacto. A taxa de liberação de Ag e V foi analisada por espectrometria de massa com plasma acoplado indutivamente (ICP-MS) e a citotoxicidade, pelo método do MTT. Análise estatística descritiva foi realizada para o teste microbiológico. Os dados das análises mecânicas foram analisados por ANOVA de 2 fatores com múltiplas comparações com ajustes de Bonferroni e os demais por Kruskal-Wallis seguido pelo pós teste de Dunn, e pelo Teste de Mann-Whitney. O nível de significância adotado foi de &alpha;=0,05. Houve diferença no padrão de dispersão promovido pelos dois métodos. O método de incorporação teve pouca influência na microbiota entretanto, o tempo de incubação e a presença de AgVO3 promoveram alterações no perfil taxonômico ao nível de filo e gênero. A adição de AgVO3 reduziu a resistência à flexão e ao impacto das resinas (p<0,001) e a técnica do filme polimérico promoveu melhor resistência à flexão (p<0,001). Maior liberação de Ag e V foi observada no grupo com 5% de AgVO3 (p<0,05). De maneira geral, não houve influência da concentração de AgVO3 e do método de incorporação na viabilidade do fibroblasto gengival humano (p>0,05) porém, o tempo de contato com os materiais foi inversamente proporcional à viabilidade (p<0,05). Conclui-se que foi possível incorporar o AgVO3 na resina acrílica por meio das duas metodologias propostas, havendo diferença no padrão de distribuição. Há diferenças na diversidade do biofilme oral inicial e maduro formado na superfície das resinas e os resultados sugerem que a incorporação de AgVO3 influencia a microbiota colonizadora. A redução das propriedades mecânicas pode ser clinicamente aceitável e os resultados da liberação elementar e da citotoxicidade não inviabilizam o uso dos materiais obtidos, embora outros testes são recomendados / This study proposed different methods of incorporating nanostructured silver vanadate (AgVO3) into an acrylic resin and evaluated the pattern of incorporation promoted, antimicrobial capacity, mechanical performance, the rate of release of silver ions (Ag) and vanadium (V) and cytotoxity. AgVO3 was incorporated in the fractions of 0-5%, by means of two methodologies, (I) Vacuum Spatulation and (II) Polymeric Film Technique. The characterization of the specimens was performed by scanning electron microscopy and microanalysis (SEM / EDS) and X-ray diffraction (XRD). The antimicrobial capacity was evaluated by genetic pyrosequencing and the mechanical performance by flexural strength and impact tests. The release rate of Ag and V was analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and cytotoxity by the MTT method. Descriptive statistical analysis was performed for the microbiological test. Data from the mechanical analyzes were analyzed by 2-way ANOVA with multiple comparisons with Bonferroni adjustments and the other by Kruskal-Wallis followed by Dunn\'s post-test and the Mann-Whitney test. The level of significance was &alpha;=0.05. There was a difference in the dispersion pattern promoted by the two methods. The incorporation method had little influence on the microbiota however, the incubation time and the presence of AgVO3 promoted changes in the taxonomic profile at the level of filo and genus. The addition of AgVO3 reduced the flexural and impact strength of the resins (p<0.001) and the polymeric film technique promoted better flexural strength (p<0.001). Greater release of Ag and V was observed in the group with 5% of AgVO3 (p<0.05). In general, there was no influence of AgVO3 concentration and incorporation method on the viability of human gingival fibroblasts (p>0.05), but the time of contact with the materials was inversely proportional to the viability (p<0.05). It was concluded that it was possible to incorporate AgVO3 into the acrylic resin by means of the two methodologies proposed, with sifference in the distribution pattern. There are differences in the diversity of the initial and mature oral biofilm formed on the surface of the resins and the results suggest that the incorporation of AgVO3 influences the colonizing microbiota. The reduction of mechanical properties may be clinically acceptable and the results of elemental release and cytotoxicity do not preclude the use of the materials obtained, although other tests are recommended

O propósito desse trabalho foi o de produzir lentes biconvexas pelo processo de injeção para serem utilizadas no ensino de óptica geométrica e de ciências nos níveis fundamental e médio. A importância de tal trabalho se justifica na carência de material experimental didático produzido no mercado nacional. Para atingir os objetivos propostos, foi necessário estudar o processo de injeção de termoplásticos e adequá-lo à produção de um componente óptico. No desenvolvimento do trabalho, foi projetado e confeccionado um molde para injeção das lentes, segundo especificações técnicas e apoiado em resultados obtidos através de simulações numéricas. Após a realização de testes de injeção, seguiu-se a caracterização das lentes obtidas através de parâmetros ópticos: transparência, birrefrigência, índice de refração, distância focal, raio de curvatura e FTM / The purpose of this work was the development and production of acrylic biconvex lens by injection process to be used in optical and science teaching at elementary and high schools. The importance of such work is based in the deficiency of experimental didactic material made in Brazil. In order to achieve the intended objective it was necessary to study the thermoplastic injection process and adapt it to the fabrication of an optical element. During the development of the work a mold was designed and constructed in according to technical specifications and based on results of numerical simulations. After the injection tests the lens were characterized by theirs optical parameters: transparency, birefringence, refraction index, focal distance, curvature radius and MFT

O presente trabalho verificou a alteração dimensional dos guias cirúrgicos confeccionados em resina acrílica para cirurgia ortognática quando submetidos à esterilização por meio de plasma de peróxido de hidrogênio. Foram utilizados 15 corpos de prova confeccionados em resina acrílica quimicamente ativada a partir de moldes metálicos em três espessuras: 1,5 mm, 3,0 mm e 5,0 mm, em um total de 45. A imagem de cada corpo de prova foi digitalizada antes e após o processo de esterilização e processada pelo programa Photoshop® CS2. Foi realizada a vetorização das imagens pelo programa Corel Trace ® 12 para mensuração pelo programa Corel Drawn ® 12. Os resultados foram submetidos ao teste estatístico dos postos sinalizados de Wilcoxon, ao nível de significância de 0,05%. Os resultados obtidos foram que nos corpos de prova de 1,5 mm de espessura não houve diferença estatisticamente significante entre as mensurações realizadas antes e após o processo de esterilização (P>0,05), porem, nas espessuras de 3,0 mm e 5,0 mm houve pelo menos uma das medidas estatisticamente diferentes (p=0,011 e p=0,017, respectivamente). Fato este que nos levou a acreditar que o processo de esterilização não leva a alteração dimensional, porem em volumes maiores provavelmente houve uma contração de polimerização diretamente proporcional. / Dimensional alterations in surgical splints made of acrylic resin used in orthognathic surgery were evaluated after hydrogen peroxide gas plasma sterilization. Fifteen specimens of resin acrylic was made by a metal model master with three different thickness: 1,5 mm, 3,0 mm and 5,0 mm, totally 45 specimens. Specimens digital image was acquired before and after sterilization and process by Photoshop® CD2 software. The images were transformed in vector form by Corel Trace® 12 software. The measures were performed by Corel Draw® 12 software. The results were submitted to Wilcoxon statistic method, 0.05 level of confidence. The results showed no statistical differences in 1.5 mm specimens (p0,307) before and after sterilization process but, in 3.0 and 5.0 mm, there was at least one measure statistically different (p=0,011 and p=0,017, respectively). It was possible to conclude that the sterilization process did not lead to dimensional alteration but, in higher thickness probably had happen a proportional polymerization contraction.

A resina acrílica para base de próteses removíveis é capaz de aderir Candida spp. sobre sua superfície, possibilitando o aparecimento das estomatites protéticas. Um fator importante para essa aderência é a hidrofobicidade do polímero. Assim, a adição de radicais hidrofílicos à resina acrílica tem potencial de torná-la menos suscetível à formação de biofilmes, e merece ser investigado. O objetivo deste projeto foi avaliar os efeitos da copolimerização do ácido metacrílico sobre aderência microbiana e propriedades físicas em um material à base de polimetil metacrilato para base de próteses removíveis. Para os ensaios com a resina acrílica, espécimes de diferentes formatos foram divididos em grupos, conforme a concentração do ácido metacrílico, em volume, na porção líquida da resina (A: 0%; B: 10%; C: 20%, D:50%). A aderência de Candida albicans foi avaliada por meio da contagem de unidades formadoras de colônia (UFC) aderidas sobre os espécimes mantidos em caldo de cultura. Também foi estudadas a dureza Vickers, a resistência flexural, a rugosidade e a estabilidade de cor. Os grupos foram descritos por média ± desvios padrão e comparados, dentro de cada variável, por meio de ANOVA, com &alpha; = 0,05. No caso da aderência de C. albicans, transformação em log10 foi realizada antes da análise. Como resultado desse estudo, não foi possível observar diferenças na aderência de C. albicans com a adição do ácido metacrílico à resina acrílica (A: 5,0 ± 0.4, B: 5,0 ± 0.4, C: 5.2 ± 0.6 e D: 5.2 ± 0.3 log10(UFC)). Redução significante foi encontrada para os valores de dureza, onde os valores (em VHN) foram A: 19,0 ± 1,4A, B: 19,6 ± 1,3A, C: 19,6 ± 0,9A e D: 14,2 ± 0,6B. Não houve diferença significante para o teste de resistência flexural (A: 96,32 ± 8,25, B: 97,65 ± 6,11, C: 102,43 ± 8,61 e D: 106,34 ± 13,69 MPa); no entanto foi observada redução na rugosidade superficial com o aumento da concentração do ácido (A: 0,26 ± 0,05A, B: 0,17 ± 0,01B, C: 0,18 ± 0,03B e D: 0,13 ± 0,03C &micro;m). Conclui-se que a copolimerização do ácido metacrílico em resina para base protética proporcionou mudanças nas propriedades físicas do material, com melhora na rugosidade, porém menor dureza. A aderência de C. albicans não sofreu interferência; futuros testes com outras espécies e na presença de proteínas salivares devem ser realizados a fim de determinar se a adição do ácido realmente possui potencial clínico. / Acrylic resins for denture base play an important role as reservoirs of micro-organisms, by increasing the risk of Candida ssp. colonization which is implicated in the pathogenesis of associated stomatitis. An important factor for this adherence is the polymer hydrophobicity. Thus, incorporation of polar radicals in the polymer could increase its hydrophylia, reducing this adherence. The main purpose of the present study was to investigate the antifungal activity of a denture base resin incorporating the methacrylic acid (MA) against Candida albicans by the counting of adherent cells and its effect on hardness, roughness and flexural strength of the material. 32 circular (14x4mm), 40 rectangular (65x10x3.3mm) and 40 square-shaped (10x10x3mm) specimens were divided into four groups, according to the concentration of MA substituted into the monomer component of a heat-polymerized acrylic resin (Lucitone 550), as follows: 0% (Control), 10%, 20% and 50% (v/v). Hardness was assessed by a hardness tester equipped with a Vickers diamond penetrator. A surface roughness tester was used to measure the surface roughness of the specimens, and a flexural strength testing was carried out on a universal testing machine. Variables were analyzed by ANOVA/Tukey\'s test (&alpha;=.05). Colonies were counted for each plated specimen and the colony-forming units per milliliter (CFU/mL) were then calculated. CFU/mL values for each concentration were compared by means of ANOVA/Tukey test after logarithmic (log 10) transformation (&alpha;=.05). A significant difference was found for hardness values (19.0±1.4A, 19.6±1.3A, 19.6±0.9A, 14.2±0.6B) VHN. Surface roughness values decreased with MA concentration increase (0.26±0.05A, 0.17±0.01AB, 0.18±0.03AB, 0.13±0.03B &micro;m). No significant difference was found for flexural strengh (96.3±8.3A, 97.7±6.1A, 102.4±8.6A, 106.3±13.7A MPa) and among the four groups for the adherence assay (A: 5,0 ± 0.4, B: 5,0 ± 0.4, C: 5.2 ± 0.6 e D: 5.2 ± 0.3 log10 (CFU). For the tested acrylic resin, the addition of MA in the concentration of 50% reduced its hardness. Thus, the presence of MA around this concentration inside the monomer may compromise the tested material structure. Although MA didnt lower the flexural strength, regardless of the concentration, the values for surface roughness reduced as MA concentration increased, suggesting that MA addition may improve the acrylic resin texture, leading to less biofilm accumulation. The adherence of C. albicans was not influenced by the presence of MA. Future tests with other microorganisms and salivary proteins should be carried out to determine if this incorporation has a clinical potencial to be used.

O objetivo principal deste trabalho foi a formação de um material que possa responder aos estímulos pH e elétrico na liberação controlada de fármaco. Assim, hidrogéis condutores foram obtidos pela combinação do hidrogel de ácido acrílico com o polímero condutor polipirrol. O polipirrol foi eletroquimicamente polimerizado no interior do hidrogel e o material obtido (AA-PPi) conservou a propriedade de intumescimento que é característico dos hidrogéis e a eletroatividade, dos polímeros condutores. Além disso, o grau de intumescimento variou com a força iônica e pH. A liberação da safranina pelo hidrogel de AA-PPi foi estudada combinando os estímulos de pH e potencial e o resultado mais interessante foi a obtenção do perfil cuja velocidade de liberação foi constante, indicando uma cinética de ordem zero. Liberação do tipo liga-desliga foi estudada com o intuito de verificar se o AA-PPi pode ser controlado por pH e/ou potencial elétrico. Foi observado que dependendo da combinação de pH e potencial, o hidrogel pode ser controlado, por variação de pH ou de potencial elétrico. Outro hidrogel sintetizado foi o do hidrogel de AA contendo o poli(3,4-etilenodioxitiofeno):poli(estireno sulfonado), este por sua vez foi polimerizado quimicamente. Porém os resultados preliminares indicaram incompatibilidade entre os dois polímeros / The aim of this work was to obtain a material that can respond to both pH and potential stimuli for drug release. Thus, eletroactive hydrogels were synthesized by the combination of the properties of acrylic acid hydrogels with the conducting polymer polypyrrole. The polypyrrole was electrochemically polymerized into the hydrogel (AA-PPi), and the material retained the swelling properties that is characteristic of hydrogels and electroactivity of conducting polymers. Furthermore, the degree of swelling varied with the ionic strength and pH. The safranin release by AA-PPi was mensured under the combination of pH and potential stimuli and the most interesting result was obtained from the linear profile indicating a zero-order kinetics. On-off release profile was studied in order to verify if the AA-PPi can be controled by pH and/or electric potential. Depending on the combination of pH or electrochemical potential, the hydrogel had pH or electrochemical control. Other hydrogel synthesized was from AA hydrogel containing poly(3,4- ethylenedioxythiophene):polystyrene sulfonate, this, in other hand, was chemically polymerized. However, preliminary results indicate incompatibility between the two polymers