The aim of this work is to study the interfacial properties of amphiphilic compounds at the liquid–air interface in an attempt to develop a comprehensive understanding of their orientation as well as the influence of their interaction with the solvent on the interfacial layer properties. Using Vibrational Sum Frequency Spectroscopy (VSFS) as the main tool, the molecular structure of the amphiphilic layer and the amphiphile–solvent relation can be illuminated in great detail – it is arguably the most sensitive surface spectroscopy currently available. Due to its second order nature, the VSFS technique is capable of distinguishing molecules at the interface even in the presence of a vast excess of similar molecules in the bulk.Ionic liquids (Ils) form a class of solvent which are increasingly receiving attention as ``green solvents´´. Some of these, such as ethyl ammonium nitrate (EAN), a protic IL, have the capacity to hydrogen bond extensively which is one of the important features they share with water. Since the interaction with solvent is an important consideration for self assembly and it is known that surfactant self assembly in the EAN bulk is analogous to in water, it was considered of interest to probe self assembly at EAN–air interface. To this end the interfacial structure of the pure EAN interface was probed, as was the conformation and ordering of nonionic surfactants. These studies reveal that EAN is highly ordered at the interface, exposing the ethyl moiety to the gas phase. Additionally, polarization studies have enabled the average orientation of the ethyl group to be determined. Adsorption of nonionic surfactants at the interface appears to significantly displace the EAN from the interface. The headgroup of the surfactant, a linear ethylene oxide group, appears to be highly disordered.The disorder of the linear ethylene oxide groups has led to difficulties in their surface spectroscopic fingerprinting in this and other works. In an attempt to study the interfacial behaviour of ethylene oxide and the temperature dependence of its hydration, closed loop structures of PEO attached to hydrophobic groups were also probed. This essentially locks their conformation. Such molecules are known as crown ethers and display interesting interfacial behaviour and also the ability to bind cations. The presence of even small amounts of adsorbed crown ethers at the water interface is shown to considerably perturb the water structure. The NO, CN, COC and CH vibrational modes of these compounds at the air-water interface as well as OH vibrational modes of the surface water hydrating this compound have been targeted in order to obtain molecular information about arrangement and conformation. The CH2 vibrational modes of crown ethers have been identified and found to be split due to their interaction with ether oxygen. The spectra provide evidence for the existence of a protonated crown complex moiety at the surface leading to the appearance of strongly ordered water species. The orientation of Nitrobenzo crown (NB15C5) was monitored as a function of solution concentration, by targeting the ratio of peak intensities of the CN and NO2 vibrational modes. The water of hydration has also been probed as a function of crown concentration, salt concentration, and temperature. The latter study strongly suggests that the surface can be treated as a charged interface, and that the associated ordered water decreases with increasing ionic strength of the bulkFinally, insoluble monolayers of fatty acids spread on a water surface have also been studied in an effort to further understand the relationship between molecular architecture and film structure. Fatty acid (Arachidic Acid – AA and Eicosenoic Acid – EA) monolayers are compared to investigate the effect on the monolayer structure of introducing unsaturation into the alkyl chain. For AA, at very large area per molecule, floating domains of crystalline nature exist rather than any classical gaseous phase. The measured conformational disorder in EA decreases continuously with monolayer compression and no crystalline domains are observed at low density. Addition of NaCl to the subphase does not affect the monolayer order for either of the compounds; instead, a dramatic increase in the signal of the water hydrating the headgroups is observed. The effect of introducing further unsaturations (up to three) was also studied in order to probe the resulting interfacial structure. Remarkably the double bonds appear to adopt the same orientation, irrespective of how many they are in the chain. By monitoring the vinyl CH stretch it was possible to study the film stability towards oxidative degradation and it was found that all three unsaturated species studied showed rapid degradation. The rate of degradation could be controlled by adjusting the film pressure. However, the monolayers could be stabilised by performing the experiments in an inert nitrogen atmosphere. / QC20100629

In this thesis a study of the factors affecting virus and virus-sized particle transport in discrete fractured dolomite rocks is presented. Physical and chemical characteristics of two fractured rocks were determined, including fracture aperture distribution, rock matrix porosity, mineral composition, and surface charge. Hydraulic and transport tests were conducted in the fractures with a conservative solute (bromide) and carboxylate-modified latex (CML) microspheres of three sizes (20, 200, and 500 nm in diameter). The earlier arrival of larger microspheres as compared to bromide indicated the effects of pore-size exclusion and preferential flow paths in the fractures. The tailing of the bromide and the smaller microsphere (20 nm) in the breakthrough curves (BTC) indicated the diffusive mass transfer between the mobile water (flowing) and immobile water (stagnant water in the low aperture areas and porous rock matrix). The effects of ionic strength and cation type on the transport of viruses (bacteriophages MS2 and PR772) and virus-sized microspheres (20 and 200 nm) were determined from the transport tests in a fracture at three levels of ionic strength (3, 5, and 12 mM) and composition (containing Na+ and/or Ca2+ ions). Retention of the microspheres and bacteriophages increased with increasing ionic strength. The addition of divalent ions (Ca2+) influenced the retention to a greater extent than monovalent ions (Na+). The effects of the aperture distribution variability, matrix diffusion, and specific discharge on the solute and microsphere transport were determined from the transport tests conducted in two fractures. The higher variability in the aperture distribution contributed to higher solute dispersion, and flow channeling as evident from the breakthrough curves for individual spatially distributed outlets. A three-dimensional model simulation of the bromide transport with varying matrix porosity identified that the porous matrix influenced the solute transport. In the transport tests, retention of the microspheres decreased with increasing specific discharge in both fractures. The results of this research have helped in identifying the important factors and their effects on solute, virus, and virus-sized colloid transport in fractured dolomite rocks, which can be useful in determining the risk of pathogen contamination of water supplies in fractured dolomite rock aquifers.

Chemically and physically patterned surfaces can be used as templates to guide nano- and micro- scale particle assembly, but the design is often limited by an inability to sufficiently characterize how pattern features influence local particle-surface interactions on the order of thermal energy, kT. The research outlined in this dissertation describes comprehensive optical microscopy (i.e. evanescent wave, video) measurements and analyses of many-body and multi-dimensional interactions, dynamics and structure in inhomogeneous colloidal fluid systems. In particular, I demonstrate how non-intrusive observation of an ensemble of particles diffusing past each other and over a physically patterned surface topography can be used to obtain sensitive images of energy landscape features. I also link diffusing colloidal probe dynamics to energy landscape features, which is important for understanding the temporal imaging process and self-assembly kinetics. A complementary effort in this dissertation investigated the use of external AC electric fields to reversibly tune colloidal interactions to produce metastable ordered configurations. In addition, the electrical impedance spectra associated with colloidal assemblies formed between interfacial microelectrode gaps was measured and consistently modelled using representative equivalent circuits. Significant results from this dissertation include the synergistic use of the very same colloids as both imaging probes and building blocks in feedback controlled selfassembly on patterns. Cycling the AC field frequencies was found to be an effective way to anneal equilibrium colloidal configurations. Quantitative predictions of dominant transport mechanisms as a function of AC electric field amplitude and frequency were able to consistently explain the steady-state colloidal microstructures formed within electrode gaps observed using video microscopy. A functional electrical switch using gold nanoparticles was realized by reversibly forming and breaking colloidal wires between electrode gaps. Extension of the concepts developed in this dissertation suggest a general strategy to engineer the assembly of colloidal particles into ordered materials and controllable devices that provide the basis for numerous emerging technologies (e.g. photonic crystals, nanowires, reconfigurable antennas, biomimetic materials).

A large concern of the fossil fuel and renewable energy industries is the sulfur poisoning of catalysts. In the case of noble metals, such as platinum, it is seen that there is a size trend associated with the level of activity in the presence of sulfur. Smaller nanoparticles could be more tolerant due to sulfur surface vacancies. On the other hand, larger particles could have less deactivation because the sulfur is more attracted to the smaller particles and the sulfur molecules bind stronger to these smaller particles. The size effect of sulfur deactivation was investigated by testing four sizes of nanoparticles, ranging from 2 - 7 nm with and without sulfur by running an ethylene hydrogenation reaction. The synthesized particles were characterized by mass spectrometry, X - ray diffraction, and transmission electron microscopy. The 7 nm catalyst resulted in being the most sulfur tolerant due to the sulfur particles binding strongly to the smaller particles.

Hydroxyethyl starches (HES) are the most routinely used synthetic colloids during fluid resuscitation and have reported effects on coagulation. The overall goal of the investigation in this thesis was to evaluate the effects of tetrastarch administration on hemodynamic, laboratory, and hemostatic variables in healthy dogs and dogs with systemic inflammation. The objectives were to compare hemodynamic and laboratory variables in dogs receiving an isotonic crystalloid (0.9% NaCl) or tetrastarch during health and after induction of systemic inflammation; to compare the hemostatic effects of an isotonic crystalloid (0.9% NaCl) and synthetic colloid (tetrastarch) in healthy dogs and dogs with induced systemic inflammation; to compare two different protocols for TEG® activation and to determine the correlation between TEG® variables and traditional coagulation test results. Sixteen adult purpose-bred Beagles were randomized into one of two groups receiving fluid resuscitation with either 40 mL/kg IV isotonic crystalloid (0.9% NaCl) or synthetic colloid (tetrastarch) after administration of lipopolysaccharide (LPS; 5 μg/kg, IV) or an equal volume of placebo (0.9% NaCl, IV). Blood samples, for analysis, were collected at 0, 1, 2, 4, and 24 hours from the time of fluid resuscitation. After a 14-day washout period, the study was repeated such that dogs received the opposite treatment (LPS or placebo) and the same resuscitation fluid. Resuscitation with equal volumes of 0.9% NaCl and tetrastarch caused similar changes in hemodynamic and laboratory variables in dogs with LPS-induced systemic inflammation; however, larger increases in HR and blood pressure were seen within the first 2 hours following tetrastarch administration compared to 0.9% NaCl. Tetrastarch administration increased COP in all dogs, despite a decrease in TS. Tetrastarch bolus administration to dogs with LPS-induced systemic inflammation also resulted in a transient hypocoagulability characterized by a prolonged PTT, decreased clot formation speed and clot strength, and acquired type 1 von Willebrand disease. Considering the limited additional benefit of tetrastarch administration on hemodynamic variables demonstrated, as well as the transient adverse hemostatic effects of tetrastarch administration, the increased cost associated with the use of tetrastarch likely negates its use as a first line treatment during fluid resuscitation in dogs. / Pet Trust Fund

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In this thesis a study of the factors affecting virus and virus-sized particle transport in discrete fractured dolomite rocks is presented. Physical and chemical characteristics of two fractured rocks were determined, including fracture aperture distribution, rock matrix porosity, mineral composition, and surface charge. Hydraulic and transport tests were conducted in the fractures with a conservative solute (bromide) and carboxylate-modified latex (CML) microspheres of three sizes (20, 200, and 500 nm in diameter). The earlier arrival of larger microspheres as compared to bromide indicated the effects of pore-size exclusion and preferential flow paths in the fractures. The tailing of the bromide and the smaller microsphere (20 nm) in the breakthrough curves (BTC) indicated the diffusive mass transfer between the mobile water (flowing) and immobile water (stagnant water in the low aperture areas and porous rock matrix). The effects of ionic strength and cation type on the transport of viruses (bacteriophages MS2 and PR772) and virus-sized microspheres (20 and 200 nm) were determined from the transport tests in a fracture at three levels of ionic strength (3, 5, and 12 mM) and composition (containing Na+ and/or Ca2+ ions). Retention of the microspheres and bacteriophages increased with increasing ionic strength. The addition of divalent ions (Ca2+) influenced the retention to a greater extent than monovalent ions (Na+). The effects of the aperture distribution variability, matrix diffusion, and specific discharge on the solute and microsphere transport were determined from the transport tests conducted in two fractures. The higher variability in the aperture distribution contributed to higher solute dispersion, and flow channeling as evident from the breakthrough curves for individual spatially distributed outlets. A three-dimensional model simulation of the bromide transport with varying matrix porosity identified that the porous matrix influenced the solute transport. In the transport tests, retention of the microspheres decreased with increasing specific discharge in both fractures. The results of this research have helped in identifying the important factors and their effects on solute, virus, and virus-sized colloid transport in fractured dolomite rocks, which can be useful in determining the risk of pathogen contamination of water supplies in fractured dolomite rock aquifers.

Colloidal particles serve as useful building blocks for materials applications ranging from controlled band-gap materials to rationally designed drug delivery systems. Thus, developing approaches to direct the assembly and disassembly of sub-micron sized particles will be paramount to further advances in materials science engineering. This project focuses on using programmable and reversible binding between oligonucleotide strands to assemble and then disassemble polystyrene colloidal particles. It is shown that DNA-mediated assembly can be reversed at a fixed temperature using secondary oligonucleotide strands to competitively displace the primary strands linking particles together. It was found that 1) titrating the surface density of hybridizing probe strands and 2) adjusting the base length difference between primary and secondary target strands was key to successful isothermal disassembly. In order to titrate the surface density of primary probe-target duplexes, colloidal particles were conjugated with mixtures of probe strands and "diluent" strands in order to minimize the number of DNA linkages between particles. To reduce the steric interference of the diluent strands to hybridization events, diluent strands were clipped with a restriction enzyme in select cases. Kinetics studies revealed that a four to six base-length difference between primary and secondary target strands resulted in extensive competitive hybridization at secondary oligonucleotide concentrations as low as 10 nM. Importantly, it was found that the timing for release of either DNA alone or DNA-conjugated nanoparticles could be tuned through choices in the DNA sequences and concentration. Lastly, competitive hybridization was explored in select studies to drive the "shedding" of PEGylated DNA targets from microspheres to reveal underlying adhesive groups or ligands on the particle surface. Unlike prior work relying on elevated temperatures to melt DNA-linkages, this work presents an important first step towards extending DNA as a reversible assembly tool for physiological applications such as multifunctional drug delivery vehicles programmed to disassemble at targeted tissue sites such as malignant tumors.

Le procédé de granulation en voie humide nécessite l'ajout d'un agent d’enrobage ou liant, typiquement composé d'agents tensioactifs, d'eau, de plastifiant et de charge hydrophobe. Cependant, dans les procédés de granulation en voie sèche, l'agent d’enrobage est ajouté sous la forme de fines particules solides. L’objectif de ce travail est double : d’une part, examiner le comportement des particules dans les systèmes secs et aqueux aux échelles microscopique et mésoscopique, et d’autre part, développer des méthodologies prédictives permettant de choisir le liant adéquat et formuler la bonne solution d’enrobage. Dans le cadre de cette étude, nous avons utilisées l'hydroxypropyl-méthylcellulose (HPMC) et la cellulose d'éthyle (EC) comme agents d’enrobage, polyvinylpyrrolidone (PVP) et la cellulose microcristalline (MCC) généralement utilisés comme liants, l'acide stéarique (SA) qui est une charge hydrophobe, et le polyéthylène glycol (PEG) comme plastifiant. Tous ces matériaux sont largement utilisés dans les industries alimentaires et pharmaceutiques. La réussite d’une granulation dépend de l’affinité entre les particules primaires et le liant. Afin de prédire l'affinité liant-substrat en milieu sec et en milieu aqueux, nous avons comparé deux approches; la première est basée sur le travail de l'adhésion alors que la seconde s’appuie sur le concept de résistance à la traction idéale. L’équation de résistance à la traction idéale a été étendue aux systèmes ternaires dans le but de l’appliquer pour la granulation en milieu aqueux. Les approches développées ont été ensuite confrontées aux données expérimentales sur différent systèmes (composées de PVP, MCC, HPMC, SA, EC, PEG et l'eau). Nous avons ainsi trouvé que l’approche basée sur le travail d'adhésion semble donner de meilleures prédictions des affinités. Les deux approches prédisent que le HPMC est un bon liant pour le MCC. Les résultats indiquent également que le PEG a une bonne affinité avec le HPMC et le SA. Nous avons ensuite étudié la structure des agglomérats formés dans les formulations colloïdales utilisées dans les procédés d’enrobage. Pour ce faire, nous nous sommes appuyés sur des analyses expérimentales et des simulations mésoscopiques. Ces dernières reposent sur l’utilisation de la méthode de dynamique des particules dissipatives (DPD) dans laquelle les composés sont décrits comme un ensemble de billes souples (approche « coarse-grain ») interagissant selon le modèle de Flory-Huggins. Les interactions répulsives entre les billes ont été évaluées en utilisant le paramètre de solubilité (δ) calculé par simulation moléculaire tout-atome. Les résultats de simulation DPD ont été comparés aux résultats expérimentaux obtenus par plusieurs voies : cryogénique-MEB, analyse de distribution de taille de particule et par la technique DSC. Les résultats de la simulation DPD montrent que le polymère HPMC est un meilleur agent stabilisant pour le SA que le PVP et le MCC. En outre, HPMC est capable de recouvrir la particule de SA d'une couche épaisse et d’y pénétrer en profondeur, empêchant ainsi l’agglomération et la croissance des cristaux de SA. Néanmoins, HPMC est incapable de stabiliser les particules de SA lorsque celles-ci sont en quantités élevées (supérieurs à 10% (w/w)). Nous constatons également que le PEG se diffuse à l'intérieur des chaînes de HPMC entrainant l’extension de ce dernier, formant ainsi un polymère composite lisse. Les résultats expérimentaux montrent des tendances similaires; l’analyse de la distribution de taille de particule indique qu’en présence de HPMC, pour de faible pourcentages de SA (au-dessous de 10% (w/w)), la majorité des particules de SA sont inférieures à 1 μm de diamètre. Les images MEB révèlent que HPMC entoure les cristaux de SA avec un film texturé et ancre sur leur surface. / Wet granulation process requires the addition of a coating agent or binder, typically composed of surfactants, water, plasticizers and fillers. In dry granulation however, the coating agent is added to the system in the form of fine solid particles. Our goals are to investigate the particles behaviour and agglomeration mechanism in dry and aqueous systems at the micro and meso scales, and also, to develop predictive methodologies and theoretical tools of investigation allowing to choose the adequate binder and to formulate the right coating solution. In this study we chose materials widely used in food and pharmaceutical industries, including; coating agents such as Hydroxypropyl-methylcellulose (HPMC) and Ethyl cellulose (EC), binders such as Polyvinylpyrrolidone (PVP) and Microcrystalline cellulose (MCC), hydrophobic filler such as Stearic acid (SA) and plasticizer such as Polyethylene glycol (PEG). A successful granulation requires good affinity between host and guest particles. In this context, in the first part of this work, two approaches to predict the binder-substrate affinity in dry and in aqueous media were compared; one based on the work of adhesion and the other based on the ideal tensile strength. The concept of ideal tensile strength was extended to ternary systems and applied for granulation in aqueous media. The developed approaches were thereafter tested for various systems (composed of PVP, MCC, HPMC, SA, EC, PEG and water) and compared to experimental observations. Approaches yielded results in good agreement with the experimental observations, but the work of adhesion approach might give more accurate affinity predictions on the particles affinity than the ideal tensile strength approach. Both approaches predicted that HPMC is a good binder for MCC. Results also indicated that PEG has a good affinity with HPMC and SA. In a second part of our work, we used mesoscale simulations and experimental techniques to investigate the structure of agglomerates formed in aqueous colloidal formulations used in coating and granulation processes. For the simulations, dissipative particle dynamics (DPD) and a coarse-grained approach were used. In the DPD method, the compounds were described as a set of soft beads interacting according to the Flory-Huggins model. The repulsive interactions between the beads were evaluated using the solubility parameter (δ) as input, where, δ was calculated by all-atom molecular simulations. The mesoscale simulation results were compared to experimental results obtained by Cryogenic-SEM, particle size distribution analysis and DSC technique. According to the DPD simulations, HPMC polymer is a better stabilizing agent for SA than PVP and MCC. In addition, HPMC is able to cover the SA particle with a thick layer ant to adsorb in depth into its inner core, preventing SA agglomeration and crystal growth. But, for high amounts of SA (above 10% (w/w)), HPMC is unable to fully stabilize SA. We also found that PEG polymer diffuses inside HPMC chains thereby extending and softening the composite polymer. Experimental results presented similar trends; particle size distribution analysis showed that in the presence of HPMC, for low percentages of SA (below 10% (w/w)), the majority of SA particles are below 1 μm in diameter. SEM images revealed that HPMC surrounds SA crystals with a hatching textured film and anchors on their surface.