Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.

Applications in controlled release and delivery calls for a good understanding of molecular transport within the carrier material and the dominating release mechanisms. It is clear that a better understanding of hindered transport and diffusion of guest molecules is important when developing new porous materials, e.g., surfactant templated silica spheres, for biotechnological applications. Confocal laser scanning microscopy was used to quantify the bulk release and intraparticle transport of small charged fluorescent dyes, and fluorescently-tagged neutral dextran, from mesoporous silica spheres. The time dependent release and the concentration profiles within the spheres have been used to analyze the release mechanisms using appropriate models. While the small, non-adsorbing anionic dye is released following a simple diffusion driven process, the concentration of the cationic dye varies radially within the spheres after loading. The release of the cationic dye is controlled by diffusion after an initial period of rapid release, which could be due to a significant fraction of the cationic dye that remains permanently attached to the negatively charged walls of the mesoporous silica spheres. The diffusion of dextran and the resulting flat concentration profiles could be related to the complex structural feature of the cylindrical pores close to the surface, and a possible conformational change of the dextran with the concentration. The stability and leaching of a catalytic enzyme, lipase, immobilized in hydrophobilized mesoporous support has also been quantified. Colloidal monodisperse mesoporous silica spheres were synthesized and transmission electron microscopy showed that the inner pore structure display a radially extending pores. The mesoporous spheres were used as solid supports for a lipid membrane incorporated with a multi-subunit redox-driven proton pump, which was shown to remain functional. / Synthesis, functionalisation and controlled release of mesoporous materials

The efficacy Biological wastewater treatment process is largely dependent on the formation of microbial flocs and settleability before the water is released into the environment. Settleability and flocculation are reliant upon stable physicochemical parameters. Extracellular polymeric substance constituents dictate physicochemical parameters of flocs. The fluctuation of these constituents within mixed microbial flocs is poorly studied. A novel aspect of this research was the use of CLSM data to get a semi- quantitative assessment of the constituents within mixed microbial flocs. Wastewater treatment flocs were characterized for eubacterial ecology, physicochemical properties, and they were visualized through correlative microscopy. It was observed that the microbial communities from the three sampling sites exhibited significant variability in numerous physicochemical properties. Overall, these results provide a first step to examine micro-localization of physicochemical properties, architecture and processes within flocs that may help better understand the causes of floc- related inefficiencies in biological wastewater treatment. / Canadian Hemophilia Society

Nemertodermatida is a group of microscopic marine worm-like animals that live as part of the marine meiofauna in sandy or muddy sediments; one species lives commensally in a holothurian. These benthic worms were thought to disperse passively with ocean currents, resulting in little speciation and thus wide or even cosmopolitan distributions. Individuals occur in low abundance and have few light microscopically available characters, which altogether may explain why only eight species had been described between the discovery of the taxon in 1930 and this thesis. We used molecular methods to address the diversity and phylogeny of this group for the first time. In a study of two nominal species with samples from all around the world, a high degree of cryptic speciation was discovered and several new species described. Diagnoses were based on molecular data complemented by morphological characters, where available. Given the patchy geographical record it can be assumed that the majority of the biodiversity of Nemertodermatida is yet to be described. A phylogenetic study including all but three known species revealed a deep divergence between the two families of Nemertodermatida but non-monophyly of the taxon was rejected by an Approximately Unbiased test. Confocal laser scanning microscopic studies of several species show that the pattern of the body-wall musculature and the nervous system are specific for different genera. The muscular system of all species consists of a basic orthogonal grid with specific diagonal musculature and specialized muscles associated with body openings. The mouth appears to be transient feature in Nemertodermatida, developing only after hatching and being reduced again in mature worms. The nervous system is highly variable with very different ground patterns between the genera, such as an epidermal net, a centralized neuropile or a commissural brain. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4. Manuscript.</p>

Pheroid is a patented system comprising of a unique submicron emulsion type formulation. Pheroid vesicles consist mainly of plant and essential fatty acids and can entrap, transport and deliver pharmacologically active compounds and other useful molecules. The aim of this study was to show that a modulation of components and parameters is necessary to obtain the optimum formula to be used in pharmaceutical preparations. Non-optimal or non-predictable stability properties of emulsions can be limiting for the applications of emulsions (Bjerregaard et al., 2001:23). Careful consideration was given to the apparatus used during the processing along with the ratios of the various components added to the formulation and the storage conditions of the Pheroid vesicles. A preliminary study was performed to optimize the most accurate processing parameters during emulsification. The effect of emulsification rate and time, the temperature of the aqueous phase, the number of days the water phase were gassed, the concentration of the surfactant, cremophor® RH 40, used and the concentration of Vitamin F Ethyl Ester CLR added to the oil phase of the o/w emulsion has been studied. Quantification of the mean particle size, zeta potential, turbidity, pH and current values were used to characterize the emulsions. The samples were characterised after 1, 2, 3, 7, 14, 21 and 28 days of storage. The emulsions were also characterised with confocal laser scanning microscopy (CLSM) to measure the number and size and size distribution of the vesicles. After determination of the processing variables influencing the emulsion stability an accelerated stability test was conducted on a final formula. In the present study, accelerated stability testing employing elevated temperatures and relative humidity were used with good accuracy to predict long-term stability of an o/w emulsion kept at both 5 and 25 OC with 60 % relative humidity and 40 OC with 75 % relative humidity. The results of the stability tests were presented in histograms of the physical properties 24 hours, 1 month, 2 months and 3 months after preparation of the emulsion. It was concluded that Pheroid vesicles demonstrate much potential as a drug delivery system. The high stability of this formula allows its use in a wide variety of applications in the pharmaceutical industry. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.

Pheroid is a patented system comprising of a unique submicron emulsion type formulation. Pheroid vesicles consist mainly of plant and essential fatty acids and can entrap, transport and deliver pharmacologically active compounds and other useful molecules. The aim of this study was to show that a modulation of components and parameters is necessary to obtain the optimum formula to be used in pharmaceutical preparations. Non-optimal or non-predictable stability properties of emulsions can be limiting for the applications of emulsions (Bjerregaard et al., 2001:23). Careful consideration was given to the apparatus used during the processing along with the ratios of the various components added to the formulation and the storage conditions of the Pheroid vesicles. A preliminary study was performed to optimize the most accurate processing parameters during emulsification. The effect of emulsification rate and time, the temperature of the aqueous phase, the number of days the water phase were gassed, the concentration of the surfactant, cremophor® RH 40, used and the concentration of Vitamin F Ethyl Ester CLR added to the oil phase of the o/w emulsion has been studied. Quantification of the mean particle size, zeta potential, turbidity, pH and current values were used to characterize the emulsions. The samples were characterised after 1, 2, 3, 7, 14, 21 and 28 days of storage. The emulsions were also characterised with confocal laser scanning microscopy (CLSM) to measure the number and size and size distribution of the vesicles. After determination of the processing variables influencing the emulsion stability an accelerated stability test was conducted on a final formula. In the present study, accelerated stability testing employing elevated temperatures and relative humidity were used with good accuracy to predict long-term stability of an o/w emulsion kept at both 5 and 25 OC with 60 % relative humidity and 40 OC with 75 % relative humidity. The results of the stability tests were presented in histograms of the physical properties 24 hours, 1 month, 2 months and 3 months after preparation of the emulsion. It was concluded that Pheroid vesicles demonstrate much potential as a drug delivery system. The high stability of this formula allows its use in a wide variety of applications in the pharmaceutical industry. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.

Abstract Beneficial Reuse of Corrugated Paperboard in Civil Engineering Applications Gregory Michael Stone An investigation was conducted to explore the potential for reuse of corrugated paperboard. Corrugated paperboard represents a large fraction of the municipal solid waste generated and discarded in the United States. Alternative applications for reuse can provide a significant benefit by reducing the volume of waste being disposed and by reducing the use of raw materials. Four civil engineering applications were examined for potential beneficial reuse of corrugated paperboard: slurry trench construction, vertical drilling, directional drilling, and controlled low strength materials (CLSM). For the purpose of this project, corrugated paperboard was pulped and added to bentonite slurry or CLSM mixtures. Bentonite slurry mixtures were tested for viscosity, density, filtrate loss, and permeability. The behavior of the bentonite slurries was greatly influenced by interaction and interlocking of corrugate fibers; in general resulting in increased viscosity, filtrate loss, and permeability and decreased density. CLSM mixtures were tested for flow consistency, unit weight, air content, and compressive strength. CLSM mixtures prepared with corrugated paperboard showed an increased water demand due to high absorption of the corrugate. The higher water content was a significant factor contributing to decreased unit weight and compressive strength. CLSM mixtures containing corrugated paperboard also exhibited increased air contents, possibly due to entrapment of air within the corrugate pulp. Corrugated paperboard was used to successfully replace up to 27% of bentonite for slurry trench applications, 60% of bentonite for vertical drilling applications, and 59% of bentonite for directional drilling applications while maintaining acceptable engineering properties. For CLSM mixtures up to 1% of fine aggregate was replaced with corrugated paperboard while maintaining satisfactory engineering properties. Incorporation of corrugated paper board into bentonite slurry, CLSM, and drilling fluid applications provides a viable option for beneficial reuse.

The surface charges of cellulosic fibers contribute to several papermaking operations that influence the manufacture and final properties of paper. This thesis investigates the effect of the surface charges on wet-end chemistry, e.g. through the interaction of cationic polyelectrolytes with the fiber surface charges, and on the network strength of pulp suspensions. The polyelectrolyte titration method was used to investigate the interaction of the fiber charges with cationic polyelectrolytes. Techniques were developed to fluorescent label the adsorbing cationic polyelectrolyte in order to visualize the adsorption behavior. Fluorescent confocal laser scanning microscopy (CLSM) was used to determine the extent to which the cationic polyelectrolyte adsorbs into the porous fiber wall. It was shown that the polyelectrolyte charge density limits the adsorption to the surface under electrolyte-free conditions. Adsorption into the fiber wall only occurs for two conditions: 1) if the molecular mass is sufficiently low or 2) the electrolyte concentration is high enough to screen the charges along the polyelectrolyte backbone but not the interactions between the polyelectrolyte and the fiber charges. Aside from the polyelectrolyte properties, the fiber charge density contributes to the adsorption behavior of cationic polyelectrolytes. The fiber charge profile was altered by bulk and surface carboxymethylation. The electrolyte concentration at which a deviation from 1:1 stoichiometry occurs was shown to be dependent on the amount of surface charges, such that the deviation in stoichiometry occurs at a higher electrolyte concentration for pulps having a higher surface charge. A hypothesis was developed to test the conditions at which the deviation in adsorption stoichiometry occurs, which was defined as the critical electrolyte concentration (CEC). It was found that the CEC corresponded to the electrolyte concentration at which the distance between the fiber charges was on the order of the Debye length. Electron spectroscopy for chemical analysis (ESCA) was used as an independent calibration procedure to validate for which a 1:1 stoichiometry occurs. The analysis with ESCA agreed well with the polyelectrolyte titration method for measurement of fiber surface charges. When measured under appropriate conditions, i.e. electrolyte concentration and molecular properties, the fiber surface charge can accurately be measured by the polyelectrolyte titration method. The charge profiles of various pulp types and treatments were also examined. Having been established as a valid technique, the polyelectrolyte titration method was again used to measure the surface charge while conductometric titration was used to measure the total charge content. The amount of bulk and surface charges vary depending on the pulping method and type of wood, although the ratio between the bulk and surface charge (i.e. the charge ratio) is similar for chemical pulps. The mechanical pulp has a higher charge ratio because it contains more fines material than chemical pulp. Bleaching of the chemical pulp decreases the amount of bulk and surface charges, although the charge ratio remains essentially constant. However, methods such as beating or carboxymethyl cellulose (CMC) grafting are available to increase the charge ratio. The effect of the charge profile on fiber-fiber interactions was studied on both a microscopic and macroscopic level. Colloidal probe microscopy (CPM) was used to investigate the microscopic interactions between two cellulose surfaces. Cellulose surfaces, prepared by spin-coating a dissolving pulp onto silica, were used to model the fiber surface, which is too rough for surface force measurements. The charge density of the model surface was increased by CMC grafting. Results showed that increasing the surface charge density created large electrosteric repulsions, due to CMC the chains protruding out from the surface. These interactions on the microscopic scale affect the fiber network strength, which was measured with a parallel plate rheometer. When the repulsion is increased between the fibers, caused by the increase in the surface charge, fiber flocs break apart more easily due to a reduced friction between the fiber surfaces. The forces acting on the fiber network can also be mechanical in origin. The fiber length and flexibility were altered in order to study the influence of mechanical surface linking and elastic fiber bending on the fiber network strength. Using the storage modulus (G’0) as a measure of fiber network strength, longer fibers were found to create a stronger network due to an increased amount of fiber contacts. Flexible fibers have a lower network strength than stiff fibers because the fibers come to rest in a less strained position such that the the influence of elastic fiber bending on the fiber network strength is predominant. / QC 20100831

Civil engineers are at times required to stabilize sulfate bearing clay soils with calcium based stabilizers. Deleterious heaving in these stabilized soils may result over time. This dissertation addresses critical questions regarding the consequences of treating sulfate laden soils with calcium-based stabilizers. The use of a differential scanning calorimeter was introduced in this research as a tool to quantify the amount of ettringite formed in stabilized soils. The first part of this dissertation provides a case history analysis of the expansion history compared to the ettringite growth history of three controlled low strength mixtures containing fly ash with relatively high sulfate contents. Ettringite growth and measurable volume changes were monitored simultaneously for mixtures subjected to different environmental conditions. The observations verified the role of water in causing expansion when ettringite mineral is present. Sorption of water by the ettringite molecule was found to be a part of the reason for expansion. The second part of this dissertation evaluates the existence of threshold sulfate levels in soils as well as the role of soil mineralogy in defining the sensitivity of soils to sulfate-induced damage. A differential scanning calorimeter and thermodynamics based phase diagram approach are used to evaluate the role of soil minerals. The observations substantiated the difference in sensitivity of soils to ettringite formation, and also verified the existence of a threshold level of soluble sulfates in soils that can trigger substantial ettringite growth. The third part of this dissertation identifies alternative, probable mechanisms of swelling when sulfate laden soils are stabilized with lime. The swelling distress observed in stabilized soils is found to be due to one or a combination of three separate mechanisms: (1) volumetric expansion during ettringite formation, (2) water movement triggered by a high osmotic suction caused by sulfate salts, and (3) the ability of the ettringite mineral to absorb water and contribute to the swelling process.

En los últimos años se han producido cambios en los hábitos de consumo alimentario causados principalmente por un menor tiempo disponible para la preparación de las comidas y la reducción del número de personas por unidad familiar. El sector de los platos preparados se ha consolidado en el mercado, ofreciendo al consumidor productos de fácil y rápida preparación. En este contexto, el horno microondas se ha convertido en un electrodoméstico indispensable en cada hogar por su facilidad de uso y rapidez en la preparación de este tipo de productos. Las peculiaridades del calentamiento por microondas, donde la composición del propio alimento influye de manera crucial, dificulta la predicción generalizada del patrón de calentamiento en alimentos y hace necesario un estudio individualizado para cada caso en particular. Por tanto, la tendencia actual consiste en diseñar alimentos que sean aptos para el calentamiento en microondas desde la propia formulación de los mismos. En la presente tesis doctoral se estudiaron sistemas modelo tipo salsa bechamel como ejemplo de producto elaborado que se comercializa por sí solo o formando parte de platos preparados. Inicialmente, se analizó el impacto de la formulación de sistemas modelo elaborados con sal, agua y distintos hidrocoloides (almidones y carragenatos) en las propiedades intrínsecas del calentamiento en microondas (propiedades dieléctricas) y en las propiedades reológicas y microestructurales. A continuación, se analizaron las propiedades microestructurales y reológicas de salsas elaboradas con diversos almidones (nativos y modificados) con el fin de observar el comportamiento frente al calentamiento en horno microondas. Además, se analizó la estabilidad química y microestructural de salsas formuladas con diferentes proteínas (láctea o de soja) frente a un proceso de congelación-descongelación en horno microondas o convencional. Por último, se analizaron la microestructura y las propiedades dieléctricas de salsas elaboradas con diferentes grasas preparadas a diferentes velocidades de agitación. / Guardeño Expósito, LM. (2012). Optimización de la formulación de una salsa apta para calentar en microondas: estudio químico y microestructural [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/15758 / Palancia