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Thesis / Master of Applied Science (MASc)

Hema – Historical European Martial Arts – eller historisk fäktning är en relativt ny sport baserad på historiska manualer. Faktumet att Hema representerar orustad strid innebär att utrustning inte är tillräckligt bra för att både skydda och ge full rörlighet. Detta leder till många skador, särskilt skador som involverar händerna. Eftersom långsvärdet är det mest populära vapenslaget inom Hema hade detta projekt som mål att utveckla en ny handske för långsvärdsfäktning genom en användarcentrerad designprocess. En undersökning gjordes för att undersöka användarens preferenser och beteende som sedan ledde till en designbrief. Denna brief agerade sedan som grund för resten av projektet. I slutet av projektet blev en prototyp tillräckligt färdig för att påbörja tester men den kunde inte testa alla aspekter på grund av svårigheter med materialet. Alla krav från briefen kunde därför inte bemötas. Under arbetets gång framgick det att det eventuellt finns ett beteende gällande riskkompensering kopplat till utrustningen som används. Bättre skydd kanske leder till mer risktagande och hårdare hugg mot varandra och därmed fler skador. Det kan vara en idé att sänka känslan av säkerhet för att ändra beteende men allt hade behövt vidare undersökning.

The establishment of a routine of use of adhesive systems in dentistry make an essential way to seek out the best characteristics of these materials in order to optimizes the clinical results. The aim of this study was to evaluate the effect of temperature of adhesive system on bond strength to dentin. A total of 120 caries free third molars were sectioned longitudinally in order to obtain 240 hemi-teeth. They were embedded into a PVC cylinder with acrylic resin and polished with silicon carbide sandpapers in sequential decreasing in order to produce a standardized smear layer. The specimens were divided into 24 groups (n=10), and each one was treated with 4 different adhesive system (Adper Single Bond 2, 3MESPE; XP Bond, Dentsply; Stae, SDI; Admira, Voco) at 3 temperatures (5°C, 20°C e 37°C), simulating the follow conditions: refrigerator storage, environmental temperature and body temperature, respectively. Composite resin restorations were built up into a starch matrix bonded on dentin. After removal of the matrix, the samples were stored in distilled water at 37°C. The specimens were submitted to microshear test in a universal testing machine (EMIC DL 1000 Equipamentos e Sistemas de Ensaio Ltda. São José dos Pinhais, PR, Brasil) in times of storage of 24 hours and 180 days. The ANOVA indicated that factors like adhesive system (p<0,001), temperature (p<0,001) and storage time (p<0,015) affect significantly the bond strength, as well interactions between the factors. The most frequent behavior was increasement of bond strength according to the higher temperature. / Tendo em vista o uso rotineiro dos sistemas adesivos na Odontologia, a busca por melhores características destes materiais é essencial a fim de otimizar os resultados obtidos. Assim, este estudo teve por objetivo avaliar in vitro o efeito da temperatura dos sistemas adesivos sobre a resistência de união em dentina. Foram utilizados 120 terceiros molares, seccionados longitudinalmente, originando 240 hemi-dentes. Esses foram incluídos em tubos de PVC com resina acrílica e polidos com seqüência decrescente de lixas de carbeto de silício, sob refrigeração, a fim de padronizar a smear layer. Após, os espécimes foram divididos aleatoriamente em 24 grupos (n=10), e a dentina tratada com 4 sistemas adesivos (Adper Single Bond 2, 3MESPE; XP Bond, Dentsply; Stae, SDI; Admira, Voco), em 3 temperaturas, 5°C, 20°C e 37°C, simulando temperatura de acondicionamento em refrigerador, temperatura ambiente e corporal, respectivamente. Após, com uso de uma matriz de amido aderida a dentina, foram confeccionadas restaurações em resina composta Filtek Z250 (3M ESPE). Após a remoção da matriz, as amostras foram armazenadas em água destilada a 37°. Os corpos de prova foram então submetidos ao teste de microcisalhamento em uma máquina de ensaios universal (EMIC DL 1000 Equipamentos e Sistemas de Ensaio Ltda. São José dos Pinhais, PR, Brasil), metade deles após 24 horas, e a outra metade após 180 dias. A análise de variância indicou que os três fatores: adesivo (p<0,001), temperatura (p<0,001) e tempo (p=0,015) afetaram significativamente a resistência adesiva, bem como a interação entre os três fatores (F=6,41; p<0,001), sendo que o comportamento mais frequente foi a elevação das médias de resistência adesiva proporcionalmente ao aumento da temperatura.

Gluten sensitive entheropathy - celiac disease is a lifelong, genetically predisposed, immunologically mediated susceptibility to dietary wheat gluten, most frequently demonstrated by small-bowel damage and malabsorption syndrome. Strict adherence to gluten-free diet is the sole rational therapy of the disease. One of the possible therapeutic strategy for the treating of celiac disease is to utilize the synthetic polymer P(HEMA-co-SS). This polymer is capable specifically bound gliadin in gastrointestinal tract and by this way to neutralize the damaging effect of this alimentary protein on mucosa of small intestine in celiac patients. The in vitro study on human PBMC and specimens of small intestinal biopsies of celiac patients in our laboratory demonstrated that putative therapeutic ability of P(HEMA-co-SS) is substantially influenced by degree of proteolytic processing of gliadin and P(HEMA- co-SS) and also by different timing of per os administration of both components in organism. Another putative adjuvant therapy of celiac disease is employing of the beneficial probiotic bacterial strains. Our experiments were based on the findings of Prof. Y Sánz and her group demonstrating the significant differences in the composition of bacterial microflora in patients with active form of celiac disease,...

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Yes / Functional crosslinked hydrogels were prepared from 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (AA). The acid monomer was incorporated both via copolymerization and chain extension of a branching, reversible addition–fragmentation chain-transfer agent incorporated into the crosslinked polymer gel. The hydrogels were intolerant to high levels of acidic copolymerization as the acrylic acid weakened the ethylene glycol dimethacrylate (EGDMA) crosslinked network. Hydrogels made from HEMA, EGDMA and a branching RAFT agent provide the network with loose-chain end functionality that can be retained for subsequent chain extension. Traditional methods of surface functionalization have the downside of potentially creating a high volume of homopolymerization in the solution. Branching RAFT comonomers act as versatile anchor sites by which additional polymerization chain extension reactions can be carried out. Acrylic acid grafted onto HEMA–EGDMA hydrogels showed higher mechanical strength than the equivalent statistical copolymer networks and was shown to have functionality as an electrostatic binder of cationic flocculants.

Made available in DSpace on 2014-08-20T14:30:13Z (GMT). No. of bitstreams: 1 Dissertacao_Marilia_Oliveira_Barbosa.pdf: 1068284 bytes, checksum: 523346df7ee3bd1a1ce4c3ee23aff3e8 (MD5) Previous issue date: 2011-03-31 / HEMA is a monomer widely used in the adhesive systems, although the biologic performance has been found as negative it has been tried to solve this problem by testing new monomers with lower citotoxic potential. We analyzed the biocompatibility of five experimental dimethacrylate monomers: Bis-EMA 10, Bis- EMA 30, PEG 400, PEG 400 UDMA, PEG 1000. First, it was made an in vitro test using 3T3 mouse fibroblast cell culture. So, the cytotoxic test was made using primers at 20% and 2%. The dilutions were maintained in contact with the cells for a period of 24h and after the survival these cells was verified photometrically using MTT assay. After it was performed cytotoxic test with the resin bonds as follows: hese monomers were polymerized and leaving in immersion in DMEM for 24h and later the eluate obtained was inserted on the 3T3 cell for 24h. The statistical analysis was performed by Kruskal wallis method, followed by a multiple-comparison Dunn´s test (p<0.05). Second, the degree of conversion of adhesive resin was also analyzed.The results showed that related to the primers in the concentration of 2% only PEG 1000 group had no statistical difference with the control group. In the concentration of 20% there was no difference among Bis-EMA 10, PEG 1000 and the control group. Concerning to eluates there were no difference among Bis-EMA 10, PEG 400 UDMA and the control group. All monomers showed a degree of conversion similar than HEMA. Other studies are necessary using different concentrations and different cell lines because these monomers are promising in the use of adhesive systems. / HEMA é o monômero mais utilizado nos sistemas adesivos, embora o desempenho biológico venha sendo negativo está se tentando resolver este problema testando novos monômeros com menor potencial citotóxico. Analizamos a biocompatibilidade de cinco monômeros dimetacrilatos: Bis-EMA 10, Bis-EMA 30, PEG 400, PEG 400 UDMA, PEG 1000. Para analisá-los foi feito teste in vitro com cultura de células 3T3 de fibroblastos de ratos. Primeiramente, um teste citotóxico foi feito usando primers em concentrações de 2% e 20%. As diluições ficaram em contato com as células por um período de 24 horas, e a quantidade de células viáveis foi avaliada por meio de espectrofotômetro infravermelho, usando ensaio MTT. Um segundo teste foi realizado nos adesivos. Eles foram polimerizados e deixados em imersão em DMEM por 24 horas e depois o eludato obtido foi inserido nas células 3T3 por 24 horas. Os dados foram submetidos ao teste não paramétrico Kruskal Wallis seguido pelo teste complementar de Dunn´s (p<0,05).O grau de conversão dos adesivos também foi analisado. Os resultados mostram que, em relação aos primers, na concentração de 2%, PEG 1000 não apresentou diferença estatística do controle. Na concentração de 20% não houve diferença com o Bis-EMA 10 e PEG 1000. Em relação ao eludato não houve diferença estatística com o Bis-EMA 10 e PEG 400 UDMA. Todos monômeros tiveram grau de conversão similar ao HEMA. Outros estudos são necessários usando diferentes concentrações e diferentes linhagens celulares porque esses monômeros são promissores no uso em sistemas adesivos.

We have used a molecular modeling of both random and blocky sequence hydrogel networks of poly(N-vinyl-2-pyrrolidone-co-2-hydroxyethyl methacrylate) (P(VP-co-HEMA)) with a composition of VP:HEMA = 37:13 to investigate the effect of the monomeric sequence and the water content on the equilibrium structures and the mechanical and transport properties by full-atomistic molecular dynamics (MD) simulations. The degree of randomness of the monomer sequence for the random and the blocky copolymers, were 1.170 and 0.104, respectively, and the degree of polymerization was fixed at 50. The equilibrated density of the hydrogel was found to be larger for the random sequence than for the blocky sequence at low water contents (< 40 wt %), but this density difference decreased with increasing water content. The pair correlation function analysis shows that VP is more hydrophilic than HEMA and that the random sequence hydrogel is solvated more than the blocky sequence hydrogel at low water content, which disappears with increasing water content. Correspondingly, the water structure is more disrupted by the random sequence hydrogel at low water content but eventually develops the expected bulk-water-like structure with increasing water content. From mechanical deformation simulations, the stress-strain analysis showed that the VP is found to relax more efficiently, especially in the blocky sequence, so that the blocky sequence hydrogel shows less stress levels compared to the random sequence hydrogel. As the water content increases, the stress level becomes identical for both sequences. The elastic moduli of the hydrogels calculated from the constant strain energy minimization show the same trend with the stress-strain analysis. Ascorbic acid and D-glucose were used to study the effect of the monomeric sequence on the diffusion of small guest molecules within the hydrogels. By analyzing the pair correlation functions, it was found that the guest molecule has greater accessibility to the VP units than to the HEMA units with both monomeric sequences due to its higher hydrophilicity compared to the HEMA units. The monomeric sequence effect on the P(VP-co-HEMA) hydrogel is clearly observed with 20 wt % water content, but the monomeric sequence effect is significantly reduced with 40 wt % water content and disappears with 80 wt % water content. This is because the hydrophilic guest molecules are more likely to be associated with water molecules than with the polymer network at the high water content. By analyzing the mean square displacement, the displacement of the guest molecules and the inner surface area, it is also found that the guest molecule is confined in the system at 20 wt % water content, resulting in highly anomalous subdiffusion. Therefore, the diffusion of the guest molecules is directly affected by their interaction with the monomer units, the monomeric sequence and the geometrical confinement in the hydrogel at a low water content, but the monomeric sequence effect and the restriction on the diffusion of the guest molecule are significantly decreased with increasing the water content. We also investigated the de-swelling mechanisms of the surface-grafted poly(N-isopropylacrylamide) (P(NIPAAm)) brushes containing 1300 water molecules at 275 K, 290 K, 320 K, 345 K, and 370 K. We clearly observed the de-swelling of the water molecules for P(NIPAAm) above the lower critical solution temperature (LCST) (~305 K). Below the LCST, we did not observe the de-swelling of water molecules. Using the upper critical solution temperature (UCST) systems (poly(acrylamide) brushes) for comparison purposes, we did not observe the de-swelling of water molecules at a given range of temperatures. By analyzing the pair correlation functions and the coordination numbers, the de-swelling of the water molecules occurred distinctly around the isopropyl group of the P(NIPAAm) brush above the LCST because C(NIPAAm) does not offer sufficient interaction with the water molecules via the hydrogen bonding type of secondary interaction. We also found that the contribution of the N(NIPAAm)-O(water) pair is quite small because of the steric hindrance of the isopropyl group. By analyzing the change in the hydrogen bonds, the hydrogen bonds between polar groups and water molecules in the P(NIPAAm) brushes weaken with increasing temperature, which leads to the de-swelling of the water molecules out of the brushes above the LCST. Below the LCST, the change in the hydrogen bonds is not significant. Again, the contribution of the NH(NIPAAm)-water pairs is insignificant; the total number of hydrogen bonds is ~20, indicating that the interaction between the NH group and the water molecules is not significant due to steric hindrances. Lastly, we observed that the total surface area of the P(NIPAAm) brushes that is accessible to water molecules is decreased by collapsing the brushes followed by the de-swelling of water molecules above the LCST.

Hydrogels are polymeric materials that have three-dimensional polymeric networks, which are able to absorb and retain a large amount of water within their structures without being dissolved. Among the synthetic hydrogel, poly(2-hydroxylethyl methacrylate) (poly(HEMA)) has been of great interest because of its excellent biocompatibility with the three-dimensional networks. Therefore, poly(HEMA) hydrogels have been widely used in many areas, especially in biomedical and pharmaceutical areas, for such applications as packing materials in chromatography, sorbents in controlled release and drug delivery, implanting materials in tissue engineering. However, the applications of poly(HEMA) are still limited because of its weak mechanical strength and network properties. Therefore, in recent decades, the challenge of how to modify and control the polymer properties and how to build highly porous structures in it has received considerable attention because these modifications could significantly improve the performance of poly(HEMA) hydrogels for more favorable applications. Although HEMA and its polymers have been studied for more than 40 years, few reports about the preparation of micro-/nano-porous poly(HEMA) hydrogel particles and the requirements of their applications have risen. Furthermore, how to control the porous structures and the properties of HEMA copolymers have not been well understood. Accordingly, the objectives of this research were to investigate the synthesis of the porous copolymeric particles of HEMA with various comonomers (MMA, St and NVP), to characterize the porous structures and particle morphology, to simulate the synthesis process and porous characteristics, to explore the effects of the polymer compositions and the porous structures on the swelling properties, and to apply the resultant polymeric particles in the controlled release of the hydrophilic model drug. In the present studies, HEMA was copolymerized with three different comonomers, methyl methacrylate (MMA), styrene (St) and N-vinyl-2-pyrrolidone (NVP), respectively, to prepare highly porous particles crosslinked using ethylene glycol dimethacrylate (EGDMA) in the presence of 1-octanol used as a porogen by means of suspension copolymerization in an aqueous phase initiated by 2,2-azobisisobutyronitrile (AIBN). Nano-pores were observed in the present studies. The pore size and the swelling properties of these particles can be successfully controlled by changing comonomers or adjusting the crosslinker and porogen concentration. The results indicate that lower crosslinker or porogen concentration favors generating smaller pores, whereas a higher concentration of a hydrophilic comonomer, higher crosslinker concentration and higher porogen volume ratio promote the generation of larger pores. In addition, the effects of the porous structures and the network properties on the swelling properties were explored. The swelling capacity of the porous particles is reduced with an increase in the EGDMA molar concentration. However, higher porosity in the particles and higher amount of hydrophilic comonomer result in a higher swelling capacity of the particles. The gel formation and the porous characteristics of HEMA/comonomer/EGDMA systems were simulated using the mathematical models combining the reaction kinetics and the thermodynamics. It was found that the model over-predicted the experimental results of the porosity because the pores and the networks are shrunk or collapsed during the porogen removal. Therefore, the model predicts the maximum porosity that the polymeric particles can reach. If the hydrophobic contents are higher, the model gives better prediction of the porosity. It is concluded that the microporous structures of HEMA related hydrogels could be controlled by a properly designed process based on the knowledge gained via this research. The output of this research helps with a better understanding for industrial production of micro-porous hydrogels and their applications.