A técnica de polimerização em emulsão tem sido usada cada vez mais na indústria de tintas, resinas, plásticos, entre outros. Esse crescimento se deve as razões ambientais (uma vez que se utiliza água como fase contínua desta reação), também a versatilidade e a capacidade de produzir látex com diferentes propriedades para diferentes aplicações. Polímeros em emulsão são produtos por processo, isto é, suas propriedades são definidas durante a polimerização. Por isso, é importante o adequado monitoramento da reação de modo a permitir o controle das propriedades desejadas. A técnica de espectroscopia na região do infravermelho próximo (NIR), combinada com o uso de fibras óticas, é muito promissora para o monitoramento multivariável, em linha e em tempo real do processo de polimerização. O objetivo deste trabalho foi o de estudar o uso de espectroscopia NIR para o monitoramento em linha e em tempo real das concentrações de monômero e de não- voláteis (conhecido também como teor de sólidos) e da evolução do tamanho médio das partículas de látex (Dp) durante a reação de polimerização em emulsão de metacrilato de metila (MMA), em escala de laboratório e processo semi-batelada. Os modelos de calibração para estas variáveis foram obtidos experimentalmente empregando o método de regressão por mínimos quadrados parciais, PLS. Os resultados obtidos confirmaram algumas regiões espectrais do NIR indicadas em literatura como sendo adequadas na predição de monômero e Dp e revelaram -1 comportamentos espectrais ainda não explicados na região entre 10.475 e 13.000 cm , relacionados às variações no tamanho das partículas. Os resultados mostram também que é possível monitorar em linha e em tempo real a evolução do Dp e dos teores de monômero (MMA) e de não voláteis, simultaneamente em um único instrumento, utilizando modelos de calibração com bandas espectrais e pré-tratamentos distintos. / Emulsion polymerization is a largely and increasingly used technique in industrial production of paints, resins, plastics among others. This increase is due to environmental reasons (since water, rather than organic solvents is used as dispersing medium), as well as to the versatility and capacity of producing products with different properties for different applications. Emulsion polymers are products by process, i.e., the properties are mainly defined during the polymerization process. Thus, the adequate process monitoring is important for achieving the target properties. The NIR spectroscopy combined with optical fibers is a promising technique for the task of multivariable, real-time, in-line monitoring of polymerization processes. The aim of this work is the study of use of NIR spectroscopy for in-line, real time monitoring of the monomer and solids content, as well as the evolution of average size of the polymer particles (Dp), during semi-batch emulsion polymerization of methyl methacrylate in laboratory reactor. The calibration models for each of the monitored variables were obtained by applying the partial least squares regression method (PLS). The results confirmed that some NIR spectral ranges recommended in the literature are appropriate for the prediction of monomer content and Dp, and that there are spectral -1 . The results behaviors not yet explained in the region between 10475 and 13000cm also show that the in-line, the changes in Dp, monomer and polymer content can be simultaneously monitored in-line and in real time by NIR spectroscopy by using calibration models based on adequate spectral regions and distinct data pretreatments.

O objetivo deste trabalho foi o de avaliar a resistência à flexão e a quantidade de monômero residual superficial em resinas acrílicas para bases de próteses totais. Para tanto foram confeccionados corpos-de-prova nas dimensões de 2.5mm x 10mm x 65mm, utilizados em ambas as análises. Padronizou-se o processo de inclusão no qual foram empregadas muflas plásticas reforçadas por fibras de vidro. Sete grupos foram constituídos, de acordo com o tipo de processamento empregado na polimerização das resinas: Ac (Acron-MC) e Vw (Vipi-Wave) de ativação por energia de microondas; Lt (Lucitone 550 – grupo controle) e Vc (Vipi-Cril), resinas de ativação térmica convencional em banho de água aquecida no ciclo longo; Qc (QC-20), uma resina de ativação térmica em ciclo rápido e, dois grupos cuja resina era a mesma de ativação química (Vipi-Flash), processada em duas condições – à temperatura ambiente (Vf1) e, por aquecimento adicional em banho de água (Vf2). Os resultados mostraram diferenças estatisticamente significantes, onde o grupo Ac obteve as maiores médias para resistência flexural e os menores níveis de monômero liberado em relação às demais resinas. Os grupos Qc e Vf1 evidenciaram os piores resultados para ambos os testes, e a princípio, pareceu haver uma relação de causa e efeito entre, os elevados níveis de monômero residual encontrado nestes grupos, e a baixa resistência flexural observada. Verificou-se ainda que a imersão em água aquecida por 30min, da resina de ativação química, propiciou um ganho em qualidade do material para as características avaliadas. / The purpose of this work was the evaluation of flexural strength and quantity of superficial residual monomer in acrylic resin for complete denture. To perform both analyses it was developed specimens with a dimension of 2.5mm x 10mm x 65mm. The inclusion process was standardized by the use of plastic flasks reinforced with fiberglass. Seven groups were constituted in accordance with the type of resin polymerization process: Ac (Acron-MC) and Vw (Vipi-Wave) activated by microwave energy; Lt (Lucitone 550 – control group) and Vc (Vipi-Cril), conventional water bath curing cycles of heat activated acrylic resin; Qc (QC-20), fast cycle thermal activation; and two groups of self cured resin (Vipi-Flash), processed in two distinguished conditions: ambient temperature (Vf1) and additional heating in water bath (Vf2). The results have shown statistical significant differences. The Ac group had the highest mean to flexural resistance and the least level of released monomer in comparison with others resins. The Qc and Vf1 groups had the worst results for both tests. The initial conclusions showed a cause-effect relation between higher levels of residual monomer and lower flexural strength to this group. Additionally, it was verified that the immersion for 30 minutes of self cured resin in heated water gave an improvement of material quality to evaluated characteristics.

Made available in DSpace on 2014-08-20T14:30:17Z (GMT). No. of bitstreams: 1 Dissertacao_Eliana_do_Nascimento_Torre.pdf: 1908566 bytes, checksum: 7f4e5292cab07c5cd5840870b92b0df1 (MD5) Previous issue date: 2011-07-19 / Adhesive fillings are satisfactory on short-term evaluation. However, when the evaluation period of longevity of these fillings is longer, problems with the stability of the polymer formed by the adhesive system and the degradation of collagen forming the hybrid layer provoke a large decrease in the durability of this type of filling. The extracellular matrix metalloproteinases (MMPs) are enzymes, which have been associated with the degradation of collagen present at the hybrid layer. Therefore, the possibility of inhibiting the activity of these enzymes has been considered an important strategy to maintain and increase the longevity of adhesive fillings. Hence, the aim of this work is to evaluate the inhibitory potential of MMPs through the addiction of the monomers with promising characteristics reported in previous studies. These monomers have molecules known as ―kidnappers‖ of bivalent cations. This characteristic is important because the catalytic place of MMPs has zinc and calcium in its constitution. Therefore, the coordination of molecules with the catalytic place of the enzyme would be able to inhibit the activity of the MMPs. Dentine from teeth recently pulled will be used to obtain and purify the MMPs of dentine.. The analysis of MMPs inhibition will be carried out through a zymography. In case of positive results for the inhibition of MMPs, cytotoxicity and genotoxicity tests will be carried out in cellular lineages of human pulp fibroblasts apart from an immortalized lineage of fibroblasts of 3T3/NIH mice. The MTT (bromide 3-(4.5-dimethylthiazol-2-ilo)-2.5-diphenyltetrazolium) colorimetric test will be used to measure the cytotoxicity of the products tested and the test of micronucleus will be used to measure genotoxicity. In all groups the 10mM concentration induced 100% cell death. There was no difference in sensitivity in both strains. Statistically, in relation to the control group/untreated, the monomers were more cytotoxic in HPFs of groups 4 and 5. Similar results were found for the 3T3 lineage, except for group 2, which also showed statistical significance for all concentrations. There was a higher number of micronucleated cells in the groups where the two monomers of intermediate chains longer (PEG200 and PEG400 DMA) were used when compared to control. The results suggest that these two monomers are more cytotoxic and genotoxic. Most of the methacrylate monomers showed considerable but not total inhibition of MMP-2 by zymography. The exception was the PEG200 DMA, which only the concentration of 5 mM inhibited the activity of this gelatinolitic MMP / Restaurações adesivas apresentam desempenho satisfatório em avaliações de curto prazo, porém quando o período de avaliação da longevidade dessas restaurações é maior, problemas com a estabilidade do polímero formado pelo sistema adesivo e com a degradação do colágeno formador da camada híbrida, provocam uma queda expressiva na durabilidade desse tipo de restauração. As metaloproteinases da matriz extracelular (MMPs) são enzimas que têm sido associadas com a degradação do colágeno formador da camada híbrida e, por isso, a possibilidade de inibir a atividade dessas enzimas tem sido considerada uma estratégia importante para a manutenção e aumento da longevidade das restaurações adesivas. O objetivo do presente estudo foi avaliar o potencial inibitório da MMP-2 por monômeros com características promissoras relatadas na literatura relacionadas ao seu potencial inibidor de MMPs, sendo estes, EGDMA (1), TEGDMA (2), T4GDMA (3), PEG200 DMA (4) e PEG400 DMA (5). Dentina humana derivada de dentes recentemente extraídos foi utilizada para a obtenção e purificação das MMPs. O ensaio de inibição da MMP-2 foi realizado por zimografia. Testes de citotoxicidade e genotoxicidade foram realizados com uma linhagem primária de fibroblastos pulpares humanos (FPH), além de uma linhagem imortalizada de fibroblastos de camundongos 3T3/NIH. O teste colorimétrico MTT (brometo de 3-(4,5-dimetiltiazol-2-ilo)-2,5-difeniltetrazólio) foi usado para medir a citotoxicidade dos produtos testados, enquanto que o teste de formação de micronúcleos foi usado para avaliar a genotoxicidade. Em todos os grupos a concentração de 10mM induziu a 100% de morte celular. Não houve diferença de sensibilidade nas duas linhagens estudadas. Estatisticamente, em relação ao grupo controle/não tratado, os monômeros foram mais citotóxicos nos FPHs nos grupos 4 e 5. Resultados semelhantes foram encontrados na linhagem 3T3, à exceção do grupo 2, que apresentou diferença estatística em todas as suas concentrações, nesta célula. Houve maior número de células micronucleadas nos grupos onde foram utilizados os dois monômeros de cadeias intermediárias mais longas (PEG200 DMA e PEG400 DMA) quando comparados ao controle, sugerindo os resultados, que estes monômeros são mais citotóxicos e genotóxicos. A maioria dos monômeros metacrilatos apresentou considerável, mas não total inibição da MMP-2 em todas as concentrações através dos ensaios de zimografia. A exceção foi o PEG200DMA, o qual somente a concentração de 5mM inibiu a atividade gelatinolítica da referida MMP

CD154 joue un rôle important dans la pathogenèse de plusieurs maladies auto-immunes, ainsi que des dysfonctionnements vasculaires. CD154 est un membre de la famille du facteur de nécrose tumorale (tumor necrosis factor, TNF) d'une importance cruciale dans l'immunité humorale. Cependant, CD154 partage également des fonctions critiques inflammatoires grâce à son interaction avec son récepteur CD40 ou des partenaires de liaison récemment identifiés, à savoir αIIbβ3, α5β1 et αMβ2. Ces réponses impliquent CD154 comme un facteur clé dans les maladies inflammatoires chroniques, notamment les maladies auto-immunes et la thrombose. L’interruption de l'interaction de CD154 avec ses récepteurs par anticorps anti-CD154 inhibe de manière significative le développement de ces maladies, bien que des effets secondaires graves ont été associés à ces traitements. Pour remédier à ces effets indésirables, d'autres approches comme des souris defficientes (Knockout), oligonucléotide antisens et ARNi ciblage ont été développés. Ces approches ont été axées sur l’interaction de CD154 avec CD40 et ne traitent pas l'interaction de CD154 avec ses autres récepteurs. Par conséquent, il existe un besoin de nouveaux traitements pour la prévention/abrogation des maladies inflammatoires ou auto-immunes qui cibles tous les récepteurs de CD154. Notre groupe a profondément étudié l'interaction structurelle/fonctionnelle de CD154 avec ses différents récepteurs. Étant donné l'importance de la structure trimérique de CD154 pour son activité biologique, nous avons généré une forme monomère de la molécule qui peut se lier spécifiquement à un récepteur sans induire l'activation intracellulaire. Cet agent est un outil thérapeutique potentiel pour le traitement de maladies reliées au CD154, tels que les événements thrombotiques. / CD154 has emerged as an important player in the pathogenesis of several autoimmune diseases, as well as vascular dysfunctions. CD154 is a member of the tumour necrosis factor family of pivotal importance in humoral immunity. However, CD154 also shares critical inflammatory functions through its interaction with its classical CD40 receptor or recently identified binding partners, namely αIIbβ3, α5β1 and αMβ2. These responses imply CD154 as a key factor in chronic inflammatory disorders including autoimmune diseases and thrombosis. Disrupting the interaction of CD154 with its receptors through anti-CD154 Abs significantly inhibits the development of these diseases, albeit serious side effects have been associated with these therapies. To overcome these adverse effects, other approaches such as knockout, antisense oligonucleotide and siRNA targeting were developed. These approaches were focused on the CD154/CD40 interaction and did not address the interaction of CD154 with its other receptors. Thus, there is a need for novel CD154 treatments for the prevention/abrogation of inflammatory or autoimmune diseases that address all CD154 receptors. Our group profoundly investigated the structural/functional interaction of CD154 with its various receptors. Given the importance of the trimeric structure of CD154 for its biological activity, we generated monomeric form of the molecule that can specifically bind to one receptor without inducing intracellular activation. This agent represents a potential therapeutic tool for the treatment of CD154-mediated diseases such as thrombotic events.

Magister Scientiae Dentium - MSc(Dent) / Resin filled dental composite materials has been introduced into dental practice since mid-1960s as an aesthetic restorative material for anterior teeth (Bowen, 1962 cited in Peutzfeldt, 1997). Since then, they have undergone several developments in order to enhance the longevity and performance of these materials. Resin filled dental composites consist of three main components namely, organic resin matrix which consists of a monomer, an initiator system and a stabilizer system, inorganic filler such as quartz, silica, etc. and coupling agent such as organo-silane coupling agent that chemically bonds the inorganic fillers to the organic resin matrix (Phillips, 1973). The properties and the performance of the resin filled dental composites are basically dependent upon the components of the materials. Some properties are related to the resin matrix, whereas others are related to the inorganic fillers and coupling agent. Furthermore, properties such as polymerization shrinkage and water sorption are dependent on both the inorganic fillers and the organic resin matrix (Asmussen, 1975; Hashinger and Fairhust, 1984; Munksgaard et al., 1987). Aim and objectives: The aim and the objectives of this study was to compare the water sorption and solubility of four bulk-fill dental resin composite materials namely, two conventional viscosity bulk-fill (Surefil bulk fill composite and Tetric N Ceram Bulk Fill) and two low viscosity bulk-fill flowable dental composite materials (Filtek Bulk Fill flowable restorative and Surefil SDR Flow). Materials and methods: Four types of bulk-fill composite restorative materials (2 bulk-fill conventional viscosity (Surefil bulk fill composite and Tetric N Ceram Bulk Fill) and 2 bulk-fill flowable low viscosity (Filtek Bulk Fill flowable restorative and Surefil SDR Flow) were used to analyse the water sorption and solubility for each resin composite type. Thirty specimens for each type of material were prepared, giving the total number of specimens to be 120 (n=120). To standardize this study Vita shade A2 was used for all the material types. All specimens were prepared in a Teflon mould with internal diameter of 15±1mm and thickness of 1±0.1mm in accordance with ISO 4049. The light curing unit used for all specimens was Elipar™ S10, (3M ESPE, Germany) at an output of 1200 mW/cm2 and used according to the manufacturer’s instructions. Prior to curing, the intensity of the light was checked using Cure Rite visible curing light meter (Caulk, USA) to ensure light output consistency between specimens and was found to be 1200 mW/cm2 . All the specimens were first removed from the Teflon mould as prepared and described previously and placed in an oven at 37 ºC until their weights were constant and these weights were recorded as m1 by using an analytic balance (OHAUS, TS400D, USA). Ten specimens of each type of resin filled composite were then immersed individually in glass containers filled with 10 ml distilled water and placed in the oven at 37±1 ºC for 24 hours, 7 days, 14 days respectively. The specimens were removed; surface water was blotted with tissue paper until free from visible moisture and weighed using the analytic balance (OHAUS, TS400D, USA). The resultant weights were recorded as m2. The specimens were then placed in a desiccator containing silica gel (Associated Chemical Enterprises, ZA) and freshly dried for two hours in an oven at 58 ºC and then weighted to obtain m3. According to Oysaed and Ruyter formula (Oysaed and Ruyter, 1986), the water sorption and solubility was calculated using the following equation: i.Water sorption (SP) = m2 -m3 / v., ii.Water solubility (SI) = m1 -m3 / v - where v is the volume of the specimen. For monomer leakage high performance liquid chromatography (HPLC) was used to identify monomers. The water that contained stored specimens was transferred to a refrigerator immediately after the specimens were removed until HPLC analysis was carried out to determine the amount of monomers that leached out of the cured composite specimens. Results: A significant difference between the materials (p<0.05, ANOVA Analysis of Variance) showed that Surefil SDR Flow composite had the lowest overall mean water sorption values (10.191) over the three time intervals (24 hrs, 7 days and 14 days) which was significantly smaller than the other means, followed by Filtek Bulk Fill flowable restorative composite (11.135) and Tetric N Ceram Bulk Fill composite (16.419). The highest water sorption mean value was recorded for Surefil bulk fill composite (21.515). The overall means of water solubility for the two bulk-fill flowables i.e. Filtek Bulk Fill flowable restorative and Surefil SDR Flow were smaller than bulk-fill conventional viscosity Surefil bulk fill and Tetric N Ceram Bulk Fill. However, all the test materials displayed no statistically significant increase in water solubility over the time period (p > 0.05 two way ANOVA test). The amounts of eluted monomers from bulk-fill conventional viscosity materials (Surefil bulk fill and Tetric N Ceram Bulk Fill) were higher than bulk-fill flowable materials (Surefil SDR Flow and Filtek Bulk Fill flowable restorative). Of all the monomers tested UDMA eluted more than Bis-GMA and TEGDMA. Overall UDMA monomer eluted the most, followed by Bis-GMA and the TEGDMA. Conclusion: Within the limitation of this study, the results of this study did not support the null hypothesis that there is no significant difference in the water sorption. The bulk-fill low viscosity flowables showed lower water sorption than the conventional viscosity bulk-fills. Surefil SDR Flow was significantly lower than the other materials followed by Filtek Bulk Fill flowable restorative and Tetric N-Ceram Bulk Fill and the highest overall means were recorded for Surefil bulk fill. For water solubility the overall means for the flowables of Filtek and SDR were smaller than Surefil and Tetric N-Ceram. For monomer elution three monomers were detected of which UDMA monomer eluted the most, followed by Bis-GMA and the TEGDMA. With regards to the elution of monomers, it was found that 3 monomers named UDMA eluted more than Bis-GMA and TEGDMA.

This diploma thesis deals with the isolation and characterization of copolymer P(3HB-co-4HB). The teoretical part was prepared as a literature search which describe polyhydroxyalkanoates in general, their structure, synthesis, degradation and isolation. Furthermore, copolymers containing 4HB units are mentioned in this thesis and there is also no mentioned of the biosynthesis and biodegradation of copolymer P(3HB-co-4HB). The first aim of this diploma thesis was to find out which solvent is the best for copolymer extraction and then characterize obtained copolymer P(3HB-co-4HB). The isolated copolymer was characterized by gas chromatography, SEC-MALS, thermal analysis and SEM. In the second part of the thesis, release of model biologically active substance from the PHA films was studied. Rhodamine 6G dye was selected for the simulation, which was used to stain the copolymer films and the P(3HB) films. It was observed that film prepared from P(3HB-co-4HB) copolymer released entrapped substance much faster than film made from P3HB homopolymer, and, in addition, the copolymer was substantially more susceptible to enzyme degradation.

No description available.

Environmental effects of selected monomers, eventually aditives of polymers, will be evaluated by ecotoxicity tests. For this purpose two alternative tests of toxicity: Thamnotoxkit F TM on testing organism Thamnocephalus platyurus and Daphnotoxkit F TM on testing organism Daphnia magna will be used. Two phytotoxicity tests will be also used: Sinapis alba root growth inhibition toxicity test and Allium cepa L root growth inhibition toxicity test. Obtained results enable calculation of value LC50, EC50 and IC50 for tested substances.

One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21797号 / 工博第4614号 / 新制||工||1719(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 杉野目 道紀, 教授 松田 建児, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM