Enhanced transport of microbes in subsurface is a focus in bioaugmentation applications for remediation of groundwater. In this study, the effect of low-concentration monorhamnolipid biosurfactant on transport of Pseudomonas aeruginosa ATCC 9027 in natural porous media (silica sand and a sandy soil) with or without hexadecane as the nonaqueous phase liquids (NAPLs) was studied with miscible-displacement experiments using artificial groundwater as the background solution. Transport of two types of cells was investigated, glucose-grown and hexadecane-grown cells with lower and higher cell surface hydrophobicity (CSH), respectively. A clean-bed colloid deposition model was used to calculate deposition rate coefficients (k) for quantitative assessment on the effect of the rhamnolipid on the transport. In the absence of NAPLs, significant cell retention was observed in the sand (81% and 82% for glucose-grown and hexadecane-grown cells, respectively). Addition of low-concentration rhamnolipid enhanced cell transport, with 40 mg/L of rhamnolipid reducing retention to 50% and 60% for glucose-grown and hexadecane-grown cells, respectively. The k values for both glucose-grown and hexadecane-grown cells correlated linearly with rhamnolipid-dependent CSH quantitatively measured using a bacterial-adhesion-to-hydrocarbon method. Retention of cells by the soil was nearly complete (>99%). Forty milligrams per liter of rhamnolipid reduced the retention to 95%. The presence of NAPLs in the sand enhanced the retention of hexadecane-grown cells with higher CSH. Transport of cells in the presence of NAPLs was enhanced by rhamnolipid at all concentrations tested, and the relative enhancement was greater than in the absence of NAPLs. This study shows the importance of hydrophobic interaction on bacterial transport in natural porous media and the potential of using low-concentration rhamnolipid for facilitating cell transport in subsurface for bioaugmentation efforts.

Soaking is an important unit operation during the processing of seeds used for direct consumption. The change in seed volume over time during soaking (volume kinetics) relates to water uptake and the quality of final product, and affects the design of the entire processing operation. Since volume determination is labor-intensive and time consuming, volume kinetics is usually not well monitored throughout seed hydration. The first chapter of this thesis is a review on the importance of soaking and volume kinetics monitoring during seed processing, the factors affecting hydration in seeds, current volume measurement methods and models used to determine and describe the change in volume over time in seeds during soaking. The second chapter describes the design, construction and evaluation of a bean volumetric auto tester (B-VAT) for volume kinetics determination of seeds during soaking. Evaluation tests suggested the system can generate reliable, reproducible, and detailed volume kinetics results for seeds soaking at different conditions with limited labor requirements. In the third chapter, the volume kinetics of 6 pinto, 5 navy and 3 black bean cultivars were tested during soaking at 25 ºC and 55 ºC. Significant differences were observed among varieties and cultivars at both temperatures (p<0.01). As temperature increased, the hydration efficiency were enhanced for all cultivars, but with various degree. In the fourth chapter, we tested the hypothesis that a thin hydrophobic layer on the seed coat was responsible of the extended initial lag phase observed during the soaking of pinto beans. Hexane pre-treatment before soaking were used for all cultivars and contact angle measurement were done to determine the surface hydrophobicity of the beans. Good correlations were found between surface hydrophobicity and hydration efficiency of beans. Hexane effectively reduced the hydrophobicity of bean surface and improved the hydration efficiency of pinto beans. The fifth chapter covers the overall conclusion of this study and states recommendations of future work regarding the improvement of the developed system and further exploration of the bean hydration process.

Soaking is an important unit operation during the processing of seeds used for direct consumption. The change in seed volume over time during soaking (volume kinetics) relates to water uptake and the quality of final product, and affects the design of the entire processing operation. Since volume determination is labor-intensive and time consuming, volume kinetics is usually not well monitored throughout seed hydration. The first chapter of this thesis is a review on the importance of soaking and volume kinetics monitoring during seed processing, the factors affecting hydration in seeds, current volume measurement methods and models used to determine and describe the change in volume over time in seeds during soaking. The second chapter describes the design, construction and evaluation of a bean volumetric auto tester (B-VAT) for volume kinetics determination of seeds during soaking. Evaluation tests suggested the system can generate reliable, reproducible, and detailed volume kinetics results for seeds soaking at different conditions with limited labor requirements. In the third chapter, the volume kinetics of 6 pinto, 5 navy and 3 black bean cultivars were tested during soaking at 25 ºC and 55 ºC. Significant differences were observed among varieties and cultivars at both temperatures (p<0.01). As temperature increased, the hydration efficiency were enhanced for all cultivars, but with various degree. In the fourth chapter, we tested the hypothesis that a thin hydrophobic layer on the seed coat was responsible of the extended initial lag phase observed during the soaking of pinto beans. Hexane pre-treatment before soaking were used for all cultivars and contact angle measurement were done to determine the surface hydrophobicity of the beans. Good correlations were found between surface hydrophobicity and hydration efficiency of beans. Hexane effectively reduced the hydrophobicity of bean surface and improved the hydration efficiency of pinto beans. The fifth chapter covers the overall conclusion of this study and states recommendations of future work regarding the improvement of the developed system and further exploration of the bean hydration process.

No description available.

Flocculation, the process whereby yeast cells attach in groups and sediment to the top or bottom of a fermenter, is industrially important in many fermentation batch operations. These batch operations include wine, distilled spirits, cider, bio-ethanol and production of commercial yeast metabolites. In the case of brewing yeast, it has been determined that flocculation occurs due to three forces called hydrophobic interactions, zymolectin binding and to a lesser extent, surface charge neutralization. This project sought to more closely study hydrophobic interactions and zymolectin binding. Earlier studies had shown that certain hydrophobic carboxylic acids, 3-OH oxylipins, formed in brewing yeast at flocculation onset. Therefore, these compounds showed potential as an indicator of overall cell surface hydrophobicity, and it was believed that flocculation level, cell surface hydrophobicity and oxylipin level would increase in unison in the yeast cell during brewing fermentations. During lab scale fermentations in shaker flasks and in a miniature fermentation assay setup, both flocculation level and cell surface hydrophobicity increased coincidently. However, 3-OH oxylipins could not be isolated from whole cells or cell wall isolates grown in the shaker flasks or whole cells grown in the miniature fermentation assay at detection limits approximated as 50 ng/0.5 g wet yeast. Due to their minute levels in brewing yeast cells, it was proposed that 3-OH oxylipins may mediate flocculation and aggregation via a quorum sensing mechanism instead of by increasing cell surface hydrophobicity. A disagreement exists in the literature where certain researchers believe zymolectin activity is induced, while others believe it is constitutive. The second part of this study attempted to address this by measuring zymolectin density during lab scale fermentations with a flow cytometer. Because of flow cytometry’s capacity for multiparametric analysis, large amounts of data were produced which gave information on not only zymolectin density, but also cell size and cellular complexity. Upon statistical analysis of the data, it was not possible to either refute or confirm the claim that zymolectin activity is induced or constitutive. However, the results suggested there could have been a population of cells with fewer zymolectins, and this certainly warrants further investigation. During the lab scale fermentations, cell size measured by a flow cytometer appeared to be correlated with manual measures of cell size. Furthermore, cell size tended towards uniformity during the fermentation which has also been observed in similar studies employing flow cytometry. Conversely, the cellular complexity of the yeast in this study did not change as in other studies by this may have been due either to strain differences or the methods used herein.

Filtration performance of mineral concentrate is mainly controlled by solid particle size and surface hydrophobicity. Filtration of coarser particles with more hydrophobic surfaces produces better filtration performance characterized by higher filtration rate (U) and lower final moisture content (FMC) in the final cake. Some filtration aids could improve filtration performance by flocculating solid particles and enhancing surface hydrophobicity. For the mineral concentrate used in this study, many filtration aids tested could only improve either U or FMC: one type was effective in improving U, and another type was effective in improving FMC. The combination of the two types of filtration aids at certain dosages could achieve better filtration performance than the optimum performance achieved by each individual filtration aid. Based on the experimental results, the working mechanism of filtration aids behind the filtration behavior was explored to deepen the understanding of the chemical-enhanced filtration of Cu/Ni concentrate. / Chemical Engineering

abstract: This paper presents a theoretical model for evaluating flashover performance of insulators under contaminated conditions. The model introduces several new features when compared with existing models such as, the formation of dry bands, variations in insulator geometry and surface wettability. The electric field distribution obtained from software for 3-Dimensional models along with form factor are used to determine the dimensions of the dry bands and the onset of arcing. The model draws heavily from experimental measurements of flashover voltage and surface resistance under wet conditions of porcelain and composite insulators. The model illustrates the dominant role played by the insulator shape and housing material on the flashover performance. / Dissertation/Thesis / M.S. Electrical Engineering 2012

Nanocrystalline diamond (NCD) films possess great mechanical properties (low friction coefficient, high hardness etc.), chemical properties (e.g. low corrosivity or chemical inertness) and good biocompatibility. This makes them perspective materials for protective coatings of medical implants and devices. As bacteria biofilms are often very resistant to antibacterial treatment, materials with anti-bacterial or at least anti-adhesive properties are needed. The interaction of NCD films with bacteria has not been properly examined yet. The aim of this thesis was to introduce and optimize the methods for routine bacterial biofilm cultivation and analysis, use them to investigate the ability of NCD films to inhibit the attachment and biofilm formation of Escherichia coli and correlate it with the NCD surface hydrophobicity. The materials used for the study were hydrogenated NCD (hydrophobic), oxidized NCD (hydrophilic) and uncoated glass. For bacterial biofilm growth, cultivation in six-well plates and continuous cultivation in CDC Bioreactor was used. Several methods were tested for quantitative biofilm detachment and analysis. The putative anti-bacterial properties of NCD material were not confirmed in this work. Higher bacterial attachment to NCD films in comparison to the uncoated glass was...

La précipitation et la dissolution du carbonate de calcium (CaCO3) sont des processus clés dans les systèmes naturels en raison de leur association intime avec le cycle du carbone terrestre. La précipitation se produit généralement sur des substrats étrangers en abaissant les barrières énergétiques qui contrôlent la nucléation. Ce processus appelé nucléation hétérogène résulte d'une interaction entre la sursaturation du fluide et les différentes énergies d’interface entre substrat-noyau-fluide. Malgré l’importance des énergies d’interface sur le devenir de la nucléation hétérogène, la littérature actuelle reste rare dans leurs valeurs absolues, limitant la précision de la modélisation du transport réactif. La formation des biominéraux constitue un réservoir majeur des carbonates dans la lithosphère. Des études récentes ont révélé des nucléations par multi-étapes impliquant la formation du carbonate de calcium amorphe (ACC), un intermédiaire métastable durant les premiers stades de la formation des biominéraux. De tels précurseurs amorphes permettent de réaliser les formes complexes des biominéraux, tandis que leur stabilité et leur cinétique de cristallisation sont contrôlées par de multiples facteurs. L'élucidation des mécanismes sous-jacents est bénéfique pour le développement de matériaux biomimétiques.Le premier objectif est de développer une compréhension prédictive des valeurs d'énergie d’interface régissant la nucléation hétérogène du CaCO3 en fonction des propriétés physico-chimiques spécifiques des substrats, comme l'hydrophobicité. Cette dernière est étudiée en utilisant de la phlogopite avec et sans substitution par le fluor produisant des substrats hydrophobes et hydrophiles. La technique de diffusion des rayons X aux petits angles en incidence rasante a été employée in situ pour obtenir des valeurs d’énergie effective d’interface. Il est intéressant de noter que les valeurs extraites pour les deux substrats sont similaires, et thermodynamiquement les deux fournissent un bon modèle pour la nucléation, alors que leurs mécanismes sont différents. La caractérisation ex situ par microscopie à force atomique a montré que le substrat hydrophile favorise la formation et la stabilisation d’ACC, tandis que le substrat hydrophobe favorise la formation de calcite. Ces résultats soulignent la flexibilité structurelle intrinsèque du CaCO3 et son avantage dans les processus de nucléation hétérogènes.Le deuxième objectif est de fournir une description atomistique de l'hydrophobicité du substrat. L'adsorption d'eau sur la phlogopite a été réalisée in situ par spectroscopie de photoélectrons à pression ambiante pour étudier l'effet de la substitution par le fluor et de différents types de contre-ions (K+, Na+ vs. Cs+). Ces résultats ont été interprétés par des simulations de dynamique moléculaire et la théorie de bond-valence. La combinaison de ces techniques montre que l'hydrophobicité du substrat provient d'une compétition entre deux facteurs: l'hydratation des contre-ions par rapport à celle du substrat.Le but final est d'étudier les mécanismes moléculaires par lesquels Mg2+, une impureté chez les précurseurs amorphes biogéniques, augmente la persistance cinétique d’ACC. La technique de diffusion inélastique incohérente des neutrons a été combinée avec la spectroscopie de corrélation de photons X pour élucider la dynamique à l'échelle nanométrique de l'eau et des ions dans les ACC. Les résultats montrent que la présence de Mg2+ augmente la diffusion atomique dans le solide tout en amplifiant la rigidité du réseau des liaisons hydrogène. Ces résultats contre-intuitifs sont abordés en considérant différents facteurs cinétiques inclus dans l’équation décrivant le taux de nucléation au sein de la théorie classique de la nucléation. Dans l'ensemble, ces résultats indiquent l'importance de l'eau comme stabilisant cinétique de la structure amorphe et de l'existence de barrières stériques qui abaissent le taux de cristallisation. / Precipitation and dissolution of calcium carbonate (CaCO3) are key processes in both natural and engineered systems due to their intimate association with the Earth’s carbon cycle. Precipitation usually occurs on foreign substrates since they lower the energetic barriers controlling nucleation events. This so-called heterogeneous nucleation results from the interplay between the fluid supersaturation and the interfacial free energies present at the substrate-nucleus-fluid interfaces. Despite the relevance of interfacial energies for the fate of heterogeneous nucleation, the current literature remains scarce in their absolute values, which limits the accuracy of reactive transport modelling. Of particular relevance to the carbon cycle, the formation of biominerals accounts for a major reservoir of the carbonate minerals in the lithosphere. Recent studies have revealed the existence of multistep nucleation pathways that involve formation of amorphous calcium carbonate (ACC), a metastable intermediate during the early stages of biomineral formation. Such amorphous precursors allow molding of the intricate shapes of biominerals, while their stability and crystallization kinetics are effectively controlled by multiple factors. Elucidating the underlying mechanisms is beneficial for the development of biomimetic materials.The first goal of this dissertation is to develop a predictive understanding of interfacial energy values governing CaCO3 heterogeneous nucleation as a function of specific physico-chemical properties of the substrates, such as hydrophobicity. This last was investigated using phlogopite, a common mica, with and without fluorine substitution yielding hydrophobic and hydrophilic substrates. In situ time-resolved Grazing-Incidence Small Angle X-ray Scattering experiments were performed to obtain effective interfacial energy values. Interestingly, the extracted values for both substrates were similar, and thermodynamically these substrates provide a good template for nucleation, but the pathways differ. By ex situ Atomic Force Microscopy characterization, the hydrophilic substrate was shown to promote the formation and stabilization of ACC, whereas the hydrophobic one favored the formation of calcite. These results point to the intrinsic structural flexibility of CaCO3 and its advantage in heterogeneous nucleation processes.The second goal is to provide an atomistic description of the substrate hydrophobicity/hydrophilicity. Water adsorption on phlogopite was studied in situ using Near-Ambient Pressure X-ray Photoelectron Spectroscopy to investigate the effect of fluorine substitution and the influence of different types of counterions (K+, Na+ vs. Cs+). The results of the spectroscopy experiments were further interpreted using molecular dynamics simulations and bond-valence theory. The combination of these techniques shows that the substrate hydrophobicity stems from a competition between two factors: hydration of counterions vs. that of substrate.The final goal is to study the molecular mechanisms by which Mg2+, a common impurity in biogenic amorphous precursors, increases the kinetic persistence of ACC. Inelastic Incoherent Neutron Scattering and X-ray Photon Correlation Spectroscopy were combined to elucidate the nanoscale dynamics of water and ions within ACC. The presence of Mg2+ was shown to enhance the atomic diffusion within the solid while simultaneously increasing the stiffness of the hydrogen bond network. These counter-intuitive results are addressed by considering the different factors included in the pre-exponential term of the nucleation rate equation within the framework of the classical nucleation theory. Overall, the results point to the importance of water as a kinetic stabilizer, and to the existence of steric barriers that lower the crystallization rate.

Les membranes cellulaires naturelles sont des structures complexes et posent de nombreux problèmes lorsqu'elles sont étudiées dans leur forme native. Par conséquent, des systèmes modèles lipidiques plus simples sont souhaitables pour étudier les composants des membranes cellulaires et leur interaction avec les molécules biologiques. Immobiliser ces modèles lipidiques sur des surfaces solides métalliques, pour former des bicouches biomimétiques supportées (SLB pour Supported Lipid Bilayer en anglais), est encore plus avantageux grâce leur adaptabilité à de nombreuses techniques de caractérisation de surface, telles que la microscopie de force atomique (AFM), la spectroscopie de résonance des plasmons de surface (SPR), l’électrochimie et les spectroscopies vibrationnelles (IR, Raman). Former ces bicouches lipidiques supportées par fusion des vésicules a toujours été la technique la plus adaptée vue sa simplicité et son efficacité. Cependant, cette technique exige des conditions expérimentales critiques comme la nécessité de surfaces planes lisses et hydrophiles (mica, verre…), des vésicules à base de phospholipides zwitterioniques en phase fluide, une concentration élevée en lipides, et une longue durée d’incubation (>1h). Dans cette thèse, nous visons à développer une nouvelle méthode simple, rapide et polyvalente permettant de former une large gamme de bicouches biomimétiques supportées, de type zwitterionique et anionique, en phase gel et fluide sur un substrat d’or. Cette nouvelle approche consiste en l’utilisation des réactions d’appariement ionique générées par un système rédox confiné en surface pour induire l’assemblage de phospholipides et former la bicouche lipidique. Le premier objectif de cette thèse est d’étudier le comportement électrochimique d’une monocouche auto-assemblée de ferrocényldodécanethiolates (FcC12SAu) en présence de molécules amphiphiles avec des groupes anioniques de types carboxyle (sel d’acide gras) et phosphate (groupes qu’on trouve dans les phospholipides) et une simple chaîne hydrocarbonée. Dans le même contexte, nous viserons également l’utilisation des réactions d’appariement ionique pour induire l’assemblage des surfactants n-alkyl carboxylate et n-alkyl phosphate à l’interface SAM/électrolyte. Le second objectif de ce travail de thèse consiste en l’utilisation du système rédox confiné en surface pour déclencher par appariement ionique l’assemblage des phospholipides (molécules amphiphiles à double chaînes hydrocarbonées) pour former des bicouches biomimétiques supportées sur une surface d’or, à partir de vésicules unilamellaires, à température ambiante et en quelques minutes. La couverture de surface en ferrocènes et l’hydrophobicité/hydrophilicité de la surface seront altérées par la suite pour investiguer l’effet sur la formation des bicouches lipidiques supportées. / Natural cell membranes are complex structures and may present many problems when studied in their native form. It is therefore desirable to have simpler lipid bilayer systems to study the components of cell membranes and their interaction with biological molecules. Immobilizing these lipid membranes on metallic solid surfaces, to form Supported Lipid Bilayers (SLB), is more advantageous due to the integrity with a wide range of surface-sensitive characterization techniques, such as atomic force microscopy (AFM), surface plasmon resonance spectroscopy (SPR), electrochemistry and vibrational spectroscopies (IR, Raman). The preparation of SLBs by vesicle fusion has always been the most suitable technique due to its simplicity and efficiency, but it requires critical experimental conditions such as the need for smooth and hydrophilic flat surfaces (mica, glass...), vesicles based on zwitterionic phospholipids in fluid phase, high lipid concentration, and lengthy SLB preparation times (>1h). In this thesis, we aim to develop a new simple, fast, and versatile method to form a wide range of supported biomimetic bilayers using zwitterionic and anionic phospholipid vesicles in gel and fluid phase on a gold substrate. This new approach consists in the use of ionic pairing reactions generated by a surface-confined redox system to induce the assembly of phospholipids and form the lipid bilayer. The first part of this thesis focuses on studying the electrochemical behavior of a self-assembled monolayer of ferrocenyldodecanethiolates (FcC12SAu) in the presence of amphiphilic molecules containing a carboxyl (fatty acid salt) and phosphate anionic group and a single hydrocarbon chain. This part will also focus on the use of ion-pairing reactions to induce the assembly of n-alkyl carboxylate and n-alkyl phosphate surfactants at the SAM/electrolyte interface. The second and main objective of this thesis work was subsequently devoted to the use of the surface-confined redox system to trigger by ion-pairing the assembly of phospholipids (amphiphilic molecules with double hydrocarbon chains) to form biomimetic bilayers supported on a gold surface from unilamellar vesicles at room temperature and within minutes. The surface coverage of ferrocenes and the hydrophobicity/hydrophilicity of the surface will be altered later to investigate the effect on the formation of supported lipid bilayers.