Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação foi estudado um processo de polimerização em emulsão de acrilonitrila, butadieno e ácido carboxílico, em escala piloto, para a produção de látex nitrílico carboxilado com alto teor de sólidos diretamente no processo reacional, sem precisar passar por etapas pós-reação de concentração. Foi estudado o efeito da temperatura, do tipo e quantidade de emulsificante, do tipo e quantidade de iniciador, do tipo de agitador e da velocidade de agitação e das etapas de adição incremental para obtenção de látex com alto teor de sólidos e a sua influência no tamanho e distribuição das partículas. Os polímeros obtidos foram caracterizados por gravimetria, usando forno de microondas para obtenção do teor de sólidos, espalhamento de luz, para determinação de tamanho e distribuição das partículas, e por espectroscopia na região do infravermelho para determinação da composição monomérica. Foi obtido polímero com até 57% de sólidos totais. O tamanho médio de partícula variou de 130 nm a 230 nm. / In this dissertation an emulsion polymerization process of acrylonitrile, butadiene and carboxylic acid was studied, in pilot scale, for the production of carboxylated nitrile latex with high solids content directly from the reaction process, without the need of post-reaction steps of concentration. It was studied the effect of temperature, type and amount of emulsifier, type and amount of initiator, type of stirring system, stirring speed and the steps of incremental additions for the production of high solid latex and its influence in the average particle size and distribution. The obtained copolymers were characterized by gravimetry using a microwave oven to determine total solids content, by light scattering in order to determine the average particle size and its distribution and by infrared spectroscopy to determine monomer composition. A latex up to 57% of total solids was obtained. The average particle size ranged from 130 nm to 230 nm.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação foi estudado um processo de polimerização em emulsão de acrilonitrila, butadieno e ácido carboxílico, em escala piloto, para a produção de látex nitrílico carboxilado com alto teor de sólidos diretamente no processo reacional, sem precisar passar por etapas pós-reação de concentração. Foi estudado o efeito da temperatura, do tipo e quantidade de emulsificante, do tipo e quantidade de iniciador, do tipo de agitador e da velocidade de agitação e das etapas de adição incremental para obtenção de látex com alto teor de sólidos e a sua influência no tamanho e distribuição das partículas. Os polímeros obtidos foram caracterizados por gravimetria, usando forno de microondas para obtenção do teor de sólidos, espalhamento de luz, para determinação de tamanho e distribuição das partículas, e por espectroscopia na região do infravermelho para determinação da composição monomérica. Foi obtido polímero com até 57% de sólidos totais. O tamanho médio de partícula variou de 130 nm a 230 nm. / In this dissertation an emulsion polymerization process of acrylonitrile, butadiene and carboxylic acid was studied, in pilot scale, for the production of carboxylated nitrile latex with high solids content directly from the reaction process, without the need of post-reaction steps of concentration. It was studied the effect of temperature, type and amount of emulsifier, type and amount of initiator, type of stirring system, stirring speed and the steps of incremental additions for the production of high solid latex and its influence in the average particle size and distribution. The obtained copolymers were characterized by gravimetry using a microwave oven to determine total solids content, by light scattering in order to determine the average particle size and its distribution and by infrared spectroscopy to determine monomer composition. A latex up to 57% of total solids was obtained. The average particle size ranged from 130 nm to 230 nm.

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This study investigated a CNF/dendrimer hydrogel and how different concentrations of the carboxylated CNF and bis-MPA ammonium dendrimer affected the hydrogels’ rheological properties. A third generation bis-MPA ammonium dendrimer was diffused into a dispersion of carboxylated cellulose nanofibrils. The CNF was carboxylated by TEMPO-oxidation and phosphate buffer deprotonating the carboxylic group. The ammonium dendrimers are cationic and, when added to the dispersion, act as a salt together with the CNF-carboxy anion creating a cationic dendrimer salt bridge. These will serve as physical crosslinks, and a CNF/dendrimer network is formed; the structure and the absorbed water make a hydrogel. Amplitude strain sweeps were performed with a rheometer to determine the gels' elastic capabilities in terms of storage modulus, G’ and loss modulus, G” as the function of the shear stress. The result shows that a higher concentration of both CNF dispersion and dendrimer yielded a higher value of the storage modulus and a lower critical strain, meaning that the hydrogel becomes firmer and less elastic. / I denna studie undersöktes en CNF/dendrimer hydrogel och hur olika koncentrationer av den karboxylerade CNF och bis-MPA ammonium dendrimer påverkar hydrogelens reologiska egenskaper. En tredje generations bis-MPA ammonium dendrimer läts diffusera i en dispersion av karboxylerade cellulosa nanofibriller (CNF). CNF karboxylerades via TEMPO-oxidation, varefter en fosfatbuffer adderades för att skapa en anjon. Dendrimerens ammoniumgrupper är katjoner och då den adderas till dispersionen kommer den agera som ett salt tillsammans med CNF-karboxyanjonen vilket skapar en katjonisk dendrimersaltbrygga. Denna agerar som en fysisk tvärbindning och skapar ett nätverk av CNF och dendrimer. Nätverket skapar tillsammans med det absorberade vattnet en hydrogel.  En amplitude strain sweep utfördes för att bestämma gelernas viskoelastiska förmåga, från mätningarna fås elasticitetsmodulen, G’ och den viskösa modulen, G’’ som funktioner av skjuvningen. Resultatet visar att en högre koncentration av CNF-dispersionen och dendrimeren leder till ett högre värde på elasticitetsmodulen samt ett lägre värde för den kritiska skjuvningen. Detta innebär att hydrogelen blir hårdare och mindre elastisk.

Throughout this thesis, we studied the biochemical and structural impact of the essential residues on the activity of class D beta-lactamases. The production of these enzymes plays a major role in the bacterial resistance. Our work is subdivided in two parts : the study of the post-translational modification of lysine 70 and the screening of new potential inhibitors for the class D β-lactamases. The first part concerns the impact of the residues tryptophan 154 and valine 117 located in the hydrophobic core. Our data indicate that the mutation of tryptophan 154 in alanine or glycine lead to a large decrease of the catalytic efficiencies of the beta-lactamase. The apo-enzyme structures of these mutants show that the lysine 70 is not carboxylated. This absence of carboxylate group induces a modification of the hydrogen network of the active site. The analysis of the complex structure of W154A-benzylpenicillin demonstrates that the deacylation step is clearly the most affected by the mutation. The mutation of tryptophan 154 in histidine leads to a slight decrease of catalytic efficiencies because the imidazol group of histidine mimics the indole group of tryptophan 154. The apo-enzyme structure reveals that lysine 70 is partially carboxylated and stabilized by an hydrogen bond between the carboxylate group and the imidazol group. In the case of the V117T mutant, a strong increase of the catalytic constant values is observed at 50 mM in NaHCO3. The structure of this mutant at pH 8.0 shows that the lysine 70 is partially carboxylated in the monomer A. The determination of individual rate constants of acylation and deacylation steps indicates that the deacylation is the limiting step for the class D beta-lactamase. The k2/k3 ratio is similar between the V117T mutant and the wild-type enzyme. The mutation of lysine 70 in alanine or cysteine leads to a large decrease of the deacylation constants inducing a poorly efficient enzyme. The obtaining of the K70C-Ampicillin complex by X-ray cristallography and the trapping of acyl-enzyme by reaction with fluorescent ampicillin are supplemental proofs that the deacylation step is the limiting rate. By crystallographic and kinetic studies, we demonstrate that the chloride inhibition of the class D beta-lactamases is due to a competition between the carboxylate group of lysine 70 and the chloride ions. At high concentration in bicarbonate, this inhibition is abolished for the wild-type enzyme. The second part of this work concerns the screening of the citrate and aminophosphonate derivated molecules for the class D beta-lactamases. In the case of OXA-10, a citrate molecule is strongly stabilized by hydrogen bonds in the active site. The benzyl esters derivatives of citrate inhibits OXA-10(KI = 20 µM) but the hydrophobic substituents are necessary to obtain a good inhibition.

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