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<p>The production of latex in a solvent-free process within a twin screw extruder is of great industrial interest given the associated reduction in environmental impact when compared to conventional solvent-based emulsification techniques. The ability to produce latex continuously is also advantageous, compared to batch-wise solvent-based processes.</p> <p>The process of solvent-free emulsification in a twin screw extruder is studied. An inline fiber optic spectroscopic system was installed in the extruder to study the residence time distribution profile of resin through the emulsification process. A design of experiment study was performed analyzing the response of latex particle size from screw speed and feed rate factors. Finally, scanning electron microscopy was used to determine the morphology of the poorly- emulsified and pre-emulsified resin.</p> <p>Experimental results demonstrate that the residence time distribution of the polymer within the extruder is largely invariant of screw speed; the system also demonstrated a very low degree of axial mixing – which was not expected but can be attributed to high degree-of-fill within the screw. The results of the design of experiments study show that the final latex particle size is more influenced by the feed rate of the polymer than the screw speed of the extruder. These results were found to be consistent with the literature based on both batch- phase inversion emulsification as well as continuous polymer blending of immiscible phases. Finally, results from a study on morphology provided evidence of water domains within the pre-inverted polymer domains, analogous to a ‘water-in-oil-in water’ dispersion. Evidence of a bicontinuous network of polymer and water was also found to exist. The summation of these experimental results leads to the hypothesis that the solvent-free emulsification process is a phase inversion-type emulsification mechanism as opposed to a direct emulsification mechanism.</p> / Master of Applied Science (MASc)

Antibiotic resistance is a worldwide threat to human health yet fewer new antibiotics are being approved. New antimicrobial drugs are urgently required. 3 Deoxy-D-manno-2-octulosonate-8-phosphate synthase (KDO8PS) is a target for antimicrobial drug design. KDO8PS catalyzes the condensation of D-arabinose-5 phosphate (A5P) with phosphoenolpyruvate (PEP) to produce KDO8P. KDO8PS catalyzes the first committed step in the lipopolysaccharides (LPS) biosynthesis pathway in Gram-negative bacteria and is critical for bacterial pathogenicity/virulence. We have characterized KDO8PS from Campylobacter jejuni (cjKDO8PS), a new metal-dependent KDO8P synthase (KDO8PS). cjKDO8PS is a tetramer in solution and optimally active at pH 7.5 and 60 °C. We have kinetically established that cjKDO8PS follows a rapid equilibrium sequential ordered ter ter kinetic mechanism, where Mn2+ binds first, followed by PEP, then A5P. Pi dissociates first, before KDO8P, then Mn2+. cjKDO8PS was inhibited by KDO8P oxime, a novel slow tight-binding inhibitor. KDO8P oxime is a competitive inhibitor with respect to PEP and A5P, but uncompetitive with respect to Mn2+, with Ki = 10 ± 1 μM and an ultimate Ki* = 0.28 ± 0.10 μM. KDO8P oxime has a residence time (tR) of 5 days on the enzyme, a parameter that is highly correlated to in vivo efficacy. Crystallization conditions for the cjKDO8PS‧Mn2+‧KDO8P oxime complex have been found and can be optimized to obtain a crystal structure that shows how KDO8P oxime interacts with the active sites. / Thesis / Doctor of Science (PhD) / The relentless increase in global antibiotic resistance is, regrettably, not matched with an increase in new effective antibiotics. New antimicrobial drug discovery strategies are desperately needed. Enzymes are key targets for drug design because they catalyze the majority of biological processes. In this project we sought to study and inhibit the activity of KDO8P synthase (KDO8PS) from Campylobacter jejuni, a common cause of food poisoning. KDO8P synthase is a critical enzyme involved in the lipopolysaccharide (LPS) biosynthesis in Gram-negative bacteria. The LPS acts as a permeability barrier and is crucial for bacterial pathogenicity/virulence. We found that C. jejuni KDO8PS is potently inhibited by KDO8P oxime, a novel inhibitor of KDO8PS. This inhibitor presents a unique opportunity to study these enzymes and a platform from which antibiotics against Gram-negative bacteria can be developed.

This dissertation focuses on the fundamental understanding of liquid dynamics confined in polymer membranes. Such knowledge guides the development of better polymer membranes for practical applications and contributes to the general understanding of confined liquid dynamics in various nanoporous materials. First, we investigate the membrane transport by experimental measurements on a PFSA membrane and computer modeling of the confined liquid molecules. We probe the nano-scale environment in the ionomer membrane by determining the activation energy of diffusion. We notice two structural features of the PFSA membrane that dominate membrane transport. At relatively high hydrations, the nano-scale phase-separation creates bulk-like water in the ionomer membrane and prompts fast transport of mobile species. At relatively low hydrations, the nanoconfinement of the polymer matrix leads to the ordering of confined water and prompts a high energy barrier for transport. We then delve deeper into the confinement effect by molecular modeling of various nanoconfining geometries, including carbon nanotubes, parallel graphene sheets, and parallel rigid rods. We notice retarded water dynamics under hydrophobic confinement regardless of the geometry. We further investigate the confined water by determining the residence time of water around water, which evaluates the timescale of associations between water molecules. We learn that a decreasing confinement size prompts longer associations among water molecules. Further, we propose that the prolonged associations are responsible for the retarded water dynamics under hydrophobic confinement. Next, we turn our attention to the effect of interactions between mobile species (mostly water molecules) and a confining surface. In ionomer membranes, interactions between mobile species and the ionic groups dominate the water-surface interactions. We start by looking at water-ion interactions in bulk solutions. Using solutions at varying concentrations, we notice a temperature-concentration superposition behavior from diffusion coefficients of water molecules and ions in the solutions in both experimental and computational results. Observation of this superposition behavior in bulk solutions is unprecedented. The temperature-concentration superposition parallels the well-known time-temperature superposition. We are able to extract the offset of reciprocal temperature, which fits well to a Williams-Landel-Ferry type equation. The temperature-concentration superposition points to the new perspective that the effect of ions on water dynamics can be similar to the effect of lowering temperature. We further investigate the effect of ions by modeling ions/charges onto confining geometries. Remarkably, we reveal that the presence of ions can break the ordered water structure induced by confinement. The hydrophobic confinement prompts the ordering of water molecules, which leads to slower diffusion and higher activation energy. The presence of ions/charges on the confining surface has multiple effects on the dynamics of confined water. First, the ions associate strongly with neighboring water molecules while breaking the hydrogen-bonding network between water molecules. Second, the disruption of the hydrogen-bonding network leads to decreased activation energy of diffusion and enhanced water mobility. At relatively high ion density, the water-ion interactions overcome the structure-breaking effect and lead to retarded water diffusion. Overall, the studies presented in this dissertation augment our understanding of water transport in nanostructures by revealing the rich behavior of liquid-water dynamics under both hydrophobic and ionic confinement. / Doctor of Philosophy / Polymer separations membranes contribute to important applications such as fuel cells and water desalination. Optimizing the separation ability of polymer membranes improves their practical performance. The transport property of a polymer membrane depends on its nanoscale and microscale structures. This dissertation focuses on the nanoscale structure-transport relations in ionic polymer membranes. We utilize nuclear magnetic resonance techniques and molecular dynamics simulations to probe the transport properties. We investigate the effects of membrane nanostructure and water-ion interactions on the dynamics of confined water. Such knowledge not only guides the development of high-performance membranes but also contributes to the fundamental understanding of liquid dynamics in nanoporous materials.

This study aims to integrate groundwater geochemistry and mathematical modeling to determine the dominant geochemical processes and groundwater residence time within the Wilcox aquifer in the northern Gulf Coastal Plain. Groundwater samples were collected and analyzed for major ion chemistry, stable isotopes (18O, 2H, and 13C), and radioisotope 36Cl content. Geochemical modeling enabled the identification of major sources and sinks of solutes in the aquifer. A two-dimensional, finite-difference, numerical model was used to determine the deep groundwater flow rate and transport of 36Cl in the aquifer. Major ion chemistry shows a chromatographic pattern along the flow path in which a gradual increase of Na+ and decrease of Ca2+ and Mg2+ is evident. The most plausible inverse models in the downgradient section of the aquifer indicate that oxidation of organic matter (OM), which may be associated with discontinuous lenses of lignite, and consequent release of CO2 sustain the reduction of Fe(III) (oxyhydr)oxides and sulfate and the dissolution of carbonate minerals (calcite and, in some instances, siderite). These processes, in turn, result in pyrite precipitation and exchange of Ca2+ for Na+ on clay-mineral surfaces. Models constrained with 13C are consistent with mole transfers between pairs of wells in close proximity, but not for the entire flow path. The observed range of δ13C of dissolved inorganic carbon (-7.3‰ to -12.4‰) is interpreted as a result of both oxidation of OM and dissolution of carbonates. Calculated values of 36Cl/Cl show an abrupt discontinuity between the upgradient and downgradient sections that was also observed in δ18O and δ2H data. The gradual enrichment of 18O and 2H along the flow path could be the result of diffusion. The distinct differences in δ18O and δ2H between the upgradient and downgradient Wilcox aquifer suggest that the latter preserves a paleoclimatic signal.

Aujourd’hui le développement de nouveaux matériaux polymères ayant de bonnes propriétés repose de plus en plus sur des procédés de mélange ou de compoundage de polymères au lieu de recourir à la synthèse de nouvelles molécules. L’action du mélange peut fortement influer sur la morphologie des matériaux polymères multi-constituants. Les extrudeuses bi-vis (TSE) sont souvent utilisées comme mélangeurs/réacteurs pour des procédés de mélange, de compoundage et d’extrusion réactive. Cependant, l’étude sur la qualité du mélange dans les TSE demeure un grand défi en raison de la complexité géométrique et du caractère transitoire de l’écoulement. Cette thèse a pour objet de développer un nouvel instrument en line pour mesurer en temps réel la distribution des temps de séjour (DTS) qui caractérise la performance du mélange axial et la capacité de convoyage de différents types d’éléments de vis basées sur l’analyse de l’écoulement transitoire et l’évaluation systématique de la théorie de mélange dans les TSE. Le mélange distributif des polymères fondus est caractérisé par la génération de l’aire des interfaces, un paramètre difficile à mesurer expérimentalement. Alors on fait appel à des simulations numériques de type CFD / The development of new materials with improved properties seems to rely nowadays more on blending and compounding than on the synthesis of chemically new polymers. Mixing may have a great effect on the morphology and structure of multi-component polymer materials. Twin-screw extruders (TSE) are widely used as mixers/reactors for blending, compounding, and reactive processing. This work aimed at developing a new instrument to measure in real time the residence time distribution (RTD) which characterizes the axial mixing and transport abilities of different screw elements based on the analysis of the transient flow pattern and systematic evaluation of mixing theory in TSE. Distributive mixing of polymer melts is characterized by the generation of interfacial area, which is experimentally much more difficult to measure. This 3D numerical simulation based on CFD is adopted

Aujourd’hui le développement de nouveaux matériaux polymères ayant de bonnes propriétés repose de plus en plus sur des procédés de mélange ou de compoundage de polymères au lieu de recourir à la synthèse de nouvelles molécules. L’action du mélange peut fortement influer sur la morphologie des matériaux polymères multi-constituants. Les extrudeuses bi-vis (TSE) sont souvent utilisées comme mélangeurs/réacteurs pour des procédés de mélange, de compoundage et d’extrusion réactive. Cependant, l’étude sur la qualité du mélange dans les TSE demeure un grand défi en raison de la complexité géométrique et du caractère transitoire de l’écoulement. Cette thèse a pour objet de développer un nouvel instrument en line pour mesurer en temps réel la distribution des temps de séjour (DTS) qui caractérise la performance du mélange axial et la capacité de convoyage de différents types d’éléments de vis basées sur l’analyse de l’écoulement transitoire et l’évaluation systématique de la théorie de mélange dans les TSE. Le mélange distributif des polymères fondus est caractérisé par la génération de l’aire des interfaces, un paramètre difficile à mesurer expérimentalement. Alors on fait appel à des simulations numériques de type CFD / The development of new materials with improved properties seems to rely nowadays more on blending and compounding than on the synthesis of chemically new polymers. Mixing may have a great effect on the morphology and structure of multi-component polymer materials. Twin-screw extruders (TSE) are widely used as mixers/reactors for blending, compounding, and reactive processing. This work aimed at developing a new instrument to measure in real time the residence time distribution (RTD) which characterizes the axial mixing and transport abilities of different screw elements based on the analysis of the transient flow pattern and systematic evaluation of mixing theory in TSE. Distributive mixing of polymer melts is characterized by the generation of interfacial area, which is experimentally much more difficult to measure. This 3D numerical simulation based on CFD is adopted

A travers l’exemple himalayen, nous étudions les mécanismes influençant la composition en osmium des sédiments durant l’érosion, le transport sédimentaire et le dépôt dans les zones estuariennes. Au niveau du bassin himalayen de la Kali Gandaki, les relations observées entre les concentrations en osmium et les quantités de carbone organique confirment le rôle important des schistes noirs appartenant aux TSS (non radiogéniques) et au LH (radiogénique) malgré leurs faibles répartitions géographiques. Cependant, la composition fortement radiogénique mesurée dans les sédiments du Gange n'est pas couplée a un enrichissement en 187Os dont la quantité moyenne est comparable à celle mesurée dans la croûte continentale. La signature isotopique du Gange résulterait d'un appauvrissement en Os non-radiogénique, témoignant d'une forte dilution par des sédiments dérivés de l'érosion des roches cristallines de l'HHC. Nous montrons à travers l’étude de sédiments estuariens que le comportement de l’osmium en contact avec l’eau de mer est complexe et des échanges sont possibles à l’interface. Le développement analytique réalisé en parallèle des études sur les sédiments a permis de documenter pour la première fois la composition en osmium des eaux souterraines. L’étude des aquifères de la plaine du Bengale montre que les eaux souterraines possèdent des concentrations en osmium significativement plus élevées que les eaux de rivière ou l’eau de mer. Si ce résultat est généralisable aux aquifères mondiaux, un flux global de l’ordre de 170 kg d’osmium par an pourrait être apporté à l’océan. Cet apport est significatif et impliquerait la réévaluation du bilan océanique mondial et une diminution significative du temps de résidence de l’osmium dans les océans. Ce résultat n’est pas anodin puisqu’il pourrait en partie réconcilier le temps de résidence estimé par bilan de masse océanique et les variations glaciaires-interglaciaires observées par le rapport 187Os/188Os dans de nombreux enregistrements marins / Using the Himalayan example, this study documents the systematics controlling the osmium composition of sediments during weathering processes, sedimentary transport and sediment deposition in tidal areas. The relationships observed between osmium concentrations and organic carbon contents in sediments of the Himalayan Kali Gandaki catchment underscore the role of black shales from the TSS (mostly unradiogenic) and LH (highly radiogenic) Himalayan units, despite their limited geographic distribution. However, the highly radiogenic composition displayed by Ganges sediments is not coupled to an enrichment in 187Os in these sediments, which on average are comparable to that of typical continental crust. Instead, the Ganges radiogenic signature results from an impoverishment in non-radiogenic osmium, reflecting a strong dilution by erosion products of crystalline rocks of the HHC unit. Moreover, based on the study of rivers in the tidal zone, we document the complex behavior of osmium at the salt/fresh water transition, potentially involving exchange between sediments and dissolved osmium. Analytical development performed concurrently with the sediment studies allowed the first measurements of groundwater osmium compositions. Groundwaters of Bengal plain aquifers have osmium contents significantly higher than those previously documented for river water or seawater. If this result can be generalized to other aquifers a global osmium groundwater flux to the ocean of about 170 kg per year could be expected. This contribution is significant and would require a reevaluation of both the osmium marine budget and the residence time of osmium in the ocean. This result could partially reconcile the diverging marine Os residence times estimated from mass balance and from glacial-interglacial variations in the 187Os/188Os marine record

Les évaluations de vulnérabilité spécifiques pour les ressources d'eau souterraine sont des méthodes SIG qui établissent des indices qualitatifs spatiaux qui déterminent la sensibilité à l'infiltration de polluants superficiels. D'autre part, les fonctions de transfert, comme la Distribution de Temps de Séjour (DTS), sont utilisées pour prévoir le changement temporel de qualité de l'eau au forage, mais ils ne permettent pas de relier les concentrations aux pratiques observées sur le bassin versant. Basé sur une approche analytique, un modèle pour le transport souterrain des produits phytosanitaires liant la vulnérabilité spécifique SIG à la DTS a été développée. L’idée étant de relier les notions de vulnérabilité aux méthodes de prédiction des chroniques de la qualité des eaux. L'outil estime la qualité de l'eau à partir de l'ensemble de données des cartes de vulnérabilité. La validation de cette méthode de vulnérabilité spécifique est possible à partir des données de suivi de la qualité de l’eau au forage. Une formulation de paramètres équivalents a été proposée pour prendre en compte les caractéristiques hydrodynamiques des compartiments de sol (zone saturée et zone non saturée). Une validation théorique de l'approche est faite à l’aide de modèles souterrain à différence finie : HYDRUS et MODFLOW. Une application a été réalisée sur l'aquifère karstique du Val d'Orléans. Elle a permis de déterminer la DTS des concentrations en pesticides dans l'eau souterraine et a mis en évidence la présence non négligeable des métabolites du métazachlore dans le forage. En même temps, le modèle DTS, lié au SIG rend possible la localisation des zones contributrices dans le bassin versant. / The specific vulnerability estimations for the groundwater resources are GIS methods that establish spatial qualitative indices which determine the sensitivity of infiltration from surface contaminants. On the other hand, the transfer functions, using the Residence Time Distribution (RTD), are used to predict temporal water quality change in a borehole, but they do not integrate the spatial variability of the land use. Based on an analytic (advection / dispersion equation) approach, a simple GIS-linked RTD model for groundwater transport has been developed. The tool estimates the water quality from the vulnerability map dataset. This method enables to validate the specific vulnerability maps with the water quality monitoring at the borehole. It links the impacts of land use with the temporal evolution of the water quality. A equivalent formulation parameters is proposed to take into account the hydrodynamic characteristics of the soil compartments (unsaturated zone and Saturated Zone). A theoretical validation of the approach is made from finite-difference groundwater models: HYDRUS and MODFLOW. Also, an application of the RTD compilation was realized on the Val d’Orléans karstic aquifer. This last methodology allowed to determine the RTD of pesticides into the groundwater and highlighted the not insignificant presence of the metabolite of the metazachlor in the groundwater drilling. At the same time, the GIS-linked RTD model makes possible the localization of the contributing zones in the watershed.