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<p>Ships, including those in the US Navy, collect oily wastewater in their bilge due to onboard cleaning and mechanical operations. Oil-in-water emulsions (O/W) are present in bilgewater, and their filtration is difficult due to surfactants provided by cleaning products. Despite cleaning efforts, over 457,000 tons of oil are discharged into the ocean every year. An often overlooked aspect of bilgewater emulsions is their evolution, as the ship's movement at sea provides extra energy that can further emulsify the collected oil. This work aims to understand the effects of motion on model bilgewater emulsions by tracking their evolution in dynamic (rocking motion) and static conditions. The model bilgewater emulsion comprises mineral oil, deionized water with 0.42 M NaCl to mimic the salinity of seawater and sodium lauryl ether sulfate and Triton X-100, as commonly found anionic and nonionic surfactants, respectively. A rocker is used to simulate a ship motion; 15 mL of emulsion were placed in 50 mL centrifuge tubes to mimic partially filled bilgewater tanks. Emulsions were characterized via laser diffraction and optical microscopy. Model bilgewater emulsions with either SLES or Triton X-100 at concentrations above 100 ppm and 500 ppm, respectively, show long-term stability in static (no-rocking) conditions up to 20 days of observation. These concentrations represent the minimum surfactant concentration needed to obtain stable emulsions under static conditions. Under dynamic conditions, the minimum surfactant concentration to obtain stable emulsions increases to 500 ppm and 1000 ppm for SLES and Triton X-100, respectively. These results mean that the ship motion can induce drop coalescence in unstable emulsions with lower surfactant concentrations. However, the drop size distributions for stable emulsions under dynamic conditions show further emulsification as the average drop size decreases. The ship motion can help further reduce the size of the emulsion drops to diameters < 2.8 µm, which are significantly harder to filter out using current methods. A bilgewater tank partially filled will likely show a higher amount of sloshing than a filled one. To understand the effects of bilgewater storage volume on emulsification, a series of dynamic experiments were carried out with samples that contained up to 100% of the centrifuge tube volume occupied by the model bilge water emulsion. Even when 100% of the centrifuge volume is occupied and sloshing is eliminated, the oil moves due to density differences, and the shear stress between fluids can induce the generation of drops < 2.8 µm. In summary, this work shows that the ship motion provides enough energy for emulsification once a minimum surfactant concentration is reached regardless of the volume of emulsion stored in the tanks. The data suggests that the best way to mitigate stable bilgewater emulsion formation is by reducing surfactant concentration.</p>

For the first time nonwoven fibrous scaffolds were electrospun from a low molar mass gemini ammonium surfactant, N,N–-didodecyl-N,N,N–,N–-tetramethyl-N,N–-ethanediyl-di-ammonium dibromide (12-2-12). Cryogenic transmission electron microscopy (cryo-TEM) and solution rheological experiments revealed micellar morphological transitions of 12-2-12 in water and water:methanol (1:1 vol). Electrospinning efforts of 12-2-12 from water did not produce fibers at any concentration, however, electrospinning 12-2-12 in water:methanol at concentrations greater than 2C* produced, hydrophilic continuous fibers with diameters between 0.9 and 7 μM. Photo-reactive surfactants were synthesized to electrospin robust surfactant membranes. Before electrospinning it was important to fundamentally understand the structure-property relationship of gemini surfactants. The thermal and solution properties were explored for a series of ammonium gemini surfactants using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and conductivity experiments. The Kraft temperature (Tk) was measured in water and water:methanol (1:1 vol) to investigate the influence of solvent on the surfactant solution properties. Other experiments investigate how associated photo-curable architectures are applicable in macromolecular architectures, to gain a fundamental understanding of how hydrogen bonding associations influence the photo-reactivity of functionalized acrylic copolymers. Novel hot melt pressure sensitive adhesives (HMPSAs) were developed from acrylic terpolymers of 2-ethylhexyl acrylate (EHA), 2-hydroxyethyl acrylate (HEA), and methyl acrylate (MA) functionalized with hydrogen bonding and photo-reactive functionalities. The synergy of hydrogen bonding and photo-reactivity resulted in higher peel values and rates of cinnamate photo-reactivity with increasing urethane concentration. Random copolymers of poly(n-butyl acrylate (nBA)-co-2-hydroxyethyl methacrylate (HEMA)) were functionalized with hydrogen bonding and photo-reactive groups to explore the photo-curing of associated macromolecular architectures. The influence of urethane hydrogen bonding on the photo-reactivity of cinnamate-functionalized acrylics was investigated with photo-rheology and UV-vis spectroscopy. Cinnamate-functionalized samples displayed an increase in modulus with exposure time, and the percentage increase in modulus decreased as the urethane content increased. The synergy of hydrogen bonding and photo-reactive groups resulted in higher rates of cinnamate photo-reactivity with increasing urethane concentration. Electrospun fibers were in situ photo-crosslinked to develop fibrous membranes from cinnamate functionalized low Tg acrylics. Electrospinning was conducted approximately 55 °C above the Tg of the cinnamate acrylate and the electrospun fibers did not retain their fibrous morphology without photo-curing. However, electrospun fibers were collected that retained their fibrous morphology and resisted flow when in situ photo-cured during electrospinning. The intermolecular photo-dimerization of cinnamates resulted in a network formation that prevented the low Tg cinnamate acrylate from flowing. / Ph. D.

Nanoparticle mediated drug delivery approaches provide potential opportunities for targeting and killing of intracellular bacteria. Among them, the porous silica nanoparticles deserve special attention due to their multifunctional properties such as high drug loading, controlled drug release and targeting of organs/cells. A review of the functional requirements of an ideal drug delivery system is provided. A general comparison between different drug delivery carriers and key issues to be addressed for intracellular drug delivery is discussed. Acid catalyzed and acid-base catalyzed, sol-gel derived, silica xerogel systems were investigated for sustained release of an aminoglycosides antimicrobial against salmonella infection in a mouse model. The release of gentamicin from the inner hollow part of the carrier is delayed. Further, the higher porosity of the acid–base catalyzed silica xerogel allows for high drug loading compared to the acid catalyzed silica xerogel system. Efficacy of these particles in killing intracellular bacteria (salmonella) was determined by administering three doses of porous silica loaded gentamicin. This proved to be useful in reducing the salmonella in the liver and spleen of infected mice. Furthermore, the presence of silanol groups provides the ability to functionalize the silica xerogel system with organic groups, poly (ethylene glycol) (PEG), to further increase the hydrophilicity of the silica xerogel matrix and to modify the drug release properties. Increase in the hydrophilicity of the matrix allows for faster drug release rate. In order to facilitate controlled drug release, magnetic porous silica xerogels were fabricated by incorporating iron particles within the porous silica. The particles were fabricated using an acid-base catalyzed sol-gel technique. The in-vitro drug release studies confirm that the release rate can be changed by the magnetic field "ON-OFF" mechanism. This novel drug release methodology combined with the property of high drug loading capacity proves to be influential in treating salmonella intracellular bacteria. The potential application of any drug delivery carrier relies on the ability to deliver the requisite drug without adversely affecting the cells over the long term. We have developed silica/calcium nanocomposites and evaluated their solubility behavior. The solubility of particles was characterized by particle size measurements for different periods of time. It was found that the solubility behaviour of the silica/calcium particles was dependent on their calcium content. The results obtained demonstrate the potential to use mesoporous silica/calcium nano-composites for drug delivery applications. The significant contribution of this research to drug delivery technology is on design and development of the novel porous core-shell silica nano-structures. This new core-shell nano-structure combines all the above mentioned properties (high drug loading, magnetic field controlled drug release, and solubility). The main aim of preparing these porous core-shell particles is to have a control over the solubility and drug release property, which is a significant phenomenon, which has not been achieved in any other drug delivery systems. The shell layer acts as a capping agent which dissolves at a controllable rate. The rate at which the shell layer dissolves depends on the composition of the particles. This shell prevents the drug "leakage" from the particles before reaching the target site. The core layer drug loading and release rate was modified by application of a magnetic field. Additionally, inclusion of the calcium ions in the core layer destabilizes the silica network and allows the particles to dissolve at an appropriate rate (which can be controlled by the concentration of the calcium ions). / Ph. D.

The development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging contaminants, the detection and quantification of chemicals used in unprecedented quantities and applications, and the extraction of compounds from complex matrices where the solvent-solute-matrix interactions are not completely understood. The three studies present analytical methods developed for emerging contaminants in complex matrices, including: fluorochemical surfactants in aqueous film-forming foams, oil dispersant surfactants in seawater, and fullerene nanomaterials in carbonaceous solids. Aqueous film-forming foams, used in military and commercial firefighting, represent environmentally-relevant commercial mixtures that contain a variety of fluorochemical surfactants. Combining the surfactant-selective ionization of fast atom bombardment mass spectrometry with high resolution mass spectrometry, chemical formulas for 11 different fluorochemical classes were identified. Then AFFF-related patents were used to determine the structures. Of the eleven classes of fluorochemicals, ten have little, if any, data on their environmental occurrence, fate, and potential impacts in the peer-reviewed literature. In addition, nine of the identified classes had either cationic or zwitterionic functionalities and are likely to have different transport properties compared to the well-studied anionic fluorochemicals, such as perfluorooctanoate. After the Deepwater Horizon oil spill in the summer of 2010, one of the emergency response methods for the mitigation of the oil's environmental impact was the use of unprecedented amounts of oil dispersant to break down the oil slick and encourage biodegradation. This event illustrated the need for rapid analytical method development in order to respond to the potential environmental disaster in a timely manner. Using large volume injection liquid chromatography with tandem mass spectrometry, an analytical method was developed for the trace analysis of the multiple dispersant surfactant classes and the potential degradation products of the primary surfactant. Limits of detection ranged from 49 ��� 3,000 ng/L. The method provided excellent recovery (86 ��� 119%) and precision (10 ��� 23% RSD), while also accommodating for the high salinity of seawater samples and analyte contamination. Despite the fact that fullerene nanomaterials have been studied for almost three decades, research is still being conducted to fully understand the environmental properties of these materials. Previous studies to extract fullerenes from environmental matrices have resulted in low efficiency, high variability, or the extraction efficiencies have gone unreported. Extraction by ultrasonication with toluene and 1-methylnaphthalene increased the recovery 5-fold of a spiked, isotopically-labeled C������ surrogate from carbon lampblack as compared to that of the conventional approach of extracting with 100% toluene. The study revealed the importance of evaluating experimental variables such as extraction solvent composition and volume, and sample mass, as they have a significant impact on the quantitative extraction of fullerenes from environmental matrices. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Aug. 15, 2012 - Aug. 15, 2013

Soils contaminated by hydrophobic organic pollutants like polycyclic aromatic hydrocarbons (PAHs) are a common concern since they are extremely difficult to remove and their potential toxicological impacts are significant. As an alternative to traditional thermal or physical treatments, soil washing and soil flushing processes appear to be conceivable and efficient approaches, especially for higher level of pollution. However, the treatment of highly loaded soil washing/flushing solutions is another challenge to overcome. In that way, a new integrated approach is suggested: soil washing/flushing processes combined to an electrochemical advanced oxidation process (EAOP) in a combination with a recirculation loop (to save extracting agents) and/or a biological post-treatment step (to minimize energy cost).Extraction efficiency of the extracting agent like hydroxypropyl-beta-cyclodextrin (HPCD) is compared to the traditional non-ionic surfactant Tween 80 in synthetic and real soil washing solutions. A new simple fluorescent sensitive and selective quantification method is developed to monitor Tween 80 oxidation. Two EAOPs were compared: electro-Fenton (EF) and anodic oxidation (AO). Platinum (Pt) (in EF process) and boron doped diamond (BDD) (in both treatment) anodes are the respective electrodes employed to recycle effluents and to consider a biological post-treatment, respectively. Regarding the extracting agent recovery, the biodegradability evolution of effluent and the energy consumption (in kWh (kgTOC)-1) during EAOP, HPCD is more advantageous than Tween 80. However, in terms of extraction efficiency, costs of extracting agents and impact on soil respirometry, Tween 80 is much more efficient. By considering all these advantages and drawbacks, Tween 80 could still appear to be the best option

Ce manuscrit se concentre sur l’étude de la dynamique de drainage de gouttes d’eau dans une phase continue d’huile de paraffine. Les gouttes sont de taille millimétrique, déformables et évoluent dans un domaine de simulation carré de 1 cm de coté. La simulation du comportement de tels systèmes pose le problème général de la description numérique des écoulements multiphasiques non stationnaires. Un modèle simplifié dans une géométrie à deux dimensions est proposé et simulé en volumes finis. Il inclut les propriétés physico-chimiques des interfaces et notamment les phénomènes de coalescence et l’évolution d’un tensioactif soluble dans les gouttes. L’effet des conditions aux limites sur le drainage d’une unique goutte est étudié. Le rôle de la coalescence sur ce drainage est également décrit pour un modèle de deux gouttes. Quelques simulations sont enfin proposées avec des systèmes dispersés plus complexes. / This manuscript focuses on the description of the settling dynamics of water droplets in a continuous phase of paraffin oil. Droplets are of millimetre size, deformable and evolve in a square simulation domain of 1 cm side. The simulations of the behaviour of such systems raise the general problem of the numerical description of the flows occurring in multiphase unsteady systems. A simplified model in a two dimensional geometry is used and integrated with a finite volume numerical technique. It includes the interfacial mechanical and chemical properties and in particular the coalescence phenomena and the evolution of a water soluble surfactant. The effect of the boundary conditions on the drainage of a unique droplet is studied. The role of drop-drop coalescence on this drainage is also described for a model with two droplets. Some simulations are finally proposed with more complex dispersed systems.

Ce travail de thèse s’inscrit dans le cadre du projet ISS/FSL/FASES dont l’objectif est de comprendre les mécanismes de vieillissement des émulsions en microgravité. Ce manuscrit est dédié à l’étude au sol des émulsions de ce projet et notamment de celles stabilisées par des mélanges tensioactifs/nanoparticules. Ces émulsions sont diluées et constituées d’une phase continue d’huile de paraffine et d’une phase dispersée aqueuse contenant un tensioactif et des nanoparticules. Leur étude et leur caractérisation est réalisée par microscopie tomographique optique et cryo-microscopie électronique à balayage. Une étude préalable de la phase dispersée permet de démontrer que les proportions respectives en tensioactif et nanoparticules modifient les propriétés rhéologiques et microscopiques de ces mélanges. Ces modifications permettent de caractériser le couplage entre les molécules tensioactives et les nanoparticules. Lorsque cette phase dispersée est émulsifiée dans l’huile de paraffine, une transition dans la morphologie des gouttes peut être mise en évidence. Les gouttes de phase dispersée présentent une topologie dépendante du ratio des concentrations en tensioactif et nanoparticules : de sphérique (pour les grandes valeurs de ce ratio) elles deviennent polymorphes (pour les petites valeurs). L’observation de ces émulsions en cryo-microscopie électronique à balayage permet de visualiser des microstructures de nanoparticules et d’expliquer l’origine de la déformation des gouttes. / This thesis is part of the ISS/FSL/FASES project which aims at understanding emulsion ageing mechanisms in microgravity. This manuscript is dedicated to the ground study of these emulsions, and particularly to those stabilized by surfactant/nanoparticles mixtures. These emulsions are diluted and composed of a paraffin oil continuous phase and an aqueous dispersed phase composed of the surfactant/particle mixtures. Emulsion characterization is performed with optical tomographic microscopy and cryo-scanning electron microscopy. A preliminary investigation of the dispersed phase shows that the proportion of surfactant and nanoparticles changes the rheological and microscopic properties of these mixtures. These changes allow the characterization of the coupling between surfactant molecules and nanoparticles. When these mixtures are emulsified in paraffin oil, a transition in the droplets morphology is evidenced. Indeed, dispersed phase droplets exhibit different shapes depending on the ratio of surfactant and nanoparticle concentrations: from spherical (for high ratios) they become polymorphous (for small ratios). Observations of these emulsions with cryo-scanning electron microscopy show the existence of nanoparticles microstructures that helps the understanding of the origin of droplets deformation.

La tuberculose reste l'une des maladies les plus meurtrières dans le monde et de nouvelles stratégies sont urgemment demandées pour combattre Mycobacterium tuberculosis (Mtb), l'agent éthiologique de la maladie. Les lipides jouent un rôle important dans le cycle de vie de la bactérie et sont largement présents dans sa membrane et son cytoplasme, où ils peuvent servir en tant que sources de carbone et d'énergie pour favoriser la pathogénicité et la survie pendant les phases d'infection et de persistance. Dans ce contexte, les rôles des enzymes lipolytiques restent mal définis et demandent à être davantage caractérisés. La première partie de ce travail de thèse a été consacrée à l'étude des douze enzymes de Mtb homologues à la lipase hormono-sensible humaine. Les effets du MmPPOX, un composé oxadiazolone très sélectif de cette famille de protéines, ont été évalués sur les enzymes recombinantes et directement in vivo sur Mtb et M. bovis BCG. Cet inhibiteur a démontré une activité antimycobactérienne, suggérant des rôles métaboliques importants pour ces enzymes. La seconde partie de ce travail a été consacrée à l'étude des mécanismes physico-chimiques dont dépendent fortement les inhibitions des lipases et des carboxylestérases in vivo, comme la présence de substrats et/ou de détergents. La spectrométrie de masse a également été introduite en tant qu'outil rapide et puissant pour caractériser les adduits [enzyme-inhibiteur]. Enfin, nous avons développé une approche de chimie protéomique pour capturer sélectivement des hydrolases à sérine à partir de milieux biologiques complexes. / Tuberculosis remains one of the deadliest diseases in the world and new strategies are urgently needed to combat Mycobacterium tuberculosis (Mtb), its etiologic agent. Lipids play an important part in the lifetime of the bacterium, as they are widely present in the membrane and stored in the cytoplasm, where they could be used as carbon and energy sources to promote pathogenicity and survival during infection and persistence. In this context, roles of lipolytic enzymes are still poorly understood and remain to be characterized. The first part of my work was devoted to the study of twelve Mtb enzymes homologous to the human hormone-sensitive lipase. Effects of MmPPOX, an oxadiazolone compound highly selective for this family of proteins, were investigated using recombinant enzymes and directly tested in vivo using Mtb and M. bovis BCG. This inhibitor demonstrated antimycobacterial activities, suggesting important metabolic roles for these enzymes. The second part of this work was devoted to the study of physico-chemical mechanisms on which lipase and carboxylesterase inhibition could strongly depend in vivo, like presence of substrates and/or detergents. Mass spectrometry was also introduced as a direct and powerful tool to characterize [enzyme-inhibitor] adducts. Finally, we developed chemical proteomics approaches to specifically capture serine hydrolases from complex biological media. We aimed to synthesize a grafted alkylphosphonate inhibitor on a solid support by assaying several grafting strategies and matrices of various chemical natures.

This thesis deals with (i) complex nanoaggregates of cationic perfluorinated surfactant N-(1,1,2,2- tetrahydroperfluorodecyl)pyridinium chloride and of double hydrophilic block polyanions poly(ethylene oxide)-b-poly(methacrylate) and poly(ethylene oxide)-b-poly((2-sulfamate-3- carboxylate)isoprene), and with (ii) mixed micelles of amphiphilic copolymer poly(ethylene oxide)- b-poly(e-caprolactone) and nonionic perfluorinated fluorosurfactant Zonyl FSN-100. The study was aimed at the characterization of the association behavior of the block copolymer-fluorosurfactant systems in aqueous solutions depending on the amount of the added surfactant, pH of the solvent and the structure of the copolymers.