xvi, 120 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / The interface between water and an organic liquid is present in a variety of biological, environmental, and chemical processes throughout science and nature. Issues such as environmental remediation and ion transport are governed by the properties of these interfaces, thus the importance of understanding them at the molecular level is apparent. The research in this dissertation shows how the structure and bonding of the liquid-liquid interface changes as the interfacial environment is altered. Vibrational sum-frequency spectroscopy (VSFS), a surface specific, non-linear optical technique, is employed for these interfacial studies. The interfacial OH stretching modes are examined using VSFS under different conditions including organic liquids of varying polarity, as well as addition of acid, base, and salts to the aqueous phase. The effects of these different conditions on the water molecules' interactions both with each other and with the non-aqueous liquid are studied in order to better characterize and understand this important system. The effect of polarity of the non-aqueous phase is presented first through investigations of different mixed halocarbon liquid-water interfaces and the neat chloroform-water interface. These studies show that as the overall polarity of the organic phase increases, the water molecules exhibit less overall orientation and undergo some weak bonding interactions with the non-aqueous liquid. Next, the influence of different salts on the water structure at the interface is studied. Examining this system shows that the dissolved ions, specifically the anions, are present within the interface and significantly alter the orientation and bonding of the interfacial water molecules. The charge, size, and polarizability of the anions all play a role in determining how the water orientation is changed within the interface. Finally, the water-like ions H 3 O + and OH - are examined at the liquid-liquid interface by changing the pH of the aqueous phase through addition of HCl or NaOH. At the extremes of the pH scale, the acid and base have ordering or disordering effects, respectively, on the water structure within the interfacial region. / Adviser: Geraldine Richmond

Propafenone is a new class 1C antiarrhythmic agent with additional calcium antagonistic and beta-blocking activities. Clinically it is effective in the treatment of supraventricular and ventricular tachycardia, atrial and ventricular fibrillation, ventricular premature contractions and for the management of Wolf-Parkinson-White syndrome. In North America it is still an investigational drug. Propafenone is a chiral drug and is used clinically in the racemic form. The enantiomers of numerous chiral drugs have been shown to differ in their disposition kinetics in the body due to their stereoselective pharmacokinetics and/or pharmacodynamic properties. Two enantiomers are thus often considered as two different entities. The relative antiarrhythmic activities of individual enantiomers of propafenone have not been studied, nor their pharmacokinetic parameters have been elucidated. In order to study the possible enantioselective role of propafenone in the body, a stereoselective assay method would be required. The present study describes the development of a sensitive and stereoselective chromatographic assay method for the simultaneous determination of the two enantiomers of propafenone in human plasma. Attempts for direct separation of the enantiomers of propafenone included several GLC and HPLC chiral stationary phases. The chiral stationary phases were a Chirasil-Valʳ GLC stationary phase, a Pirkle 2,4 dinitro-(D)-phenylglycine HPLC stationary phase and a β-cyclodextrin HPLC stationary phase. Unfortunately, these did not resolve the enantiomers of propafenone. Formation of the diastereomers with R(+)-⍺-methyl benzyl isocyanate and racemic propafenone were partially resolved on a reverse phase HPLC using a 5 u, 25 x 0.45 cm i.d. ODS column and methanol/water (70:30) as the mobile phase. However, due to the long retention time (42 min), incomplete resolution (RS=1.15) and poor sensitivity for detection (500 ng of each enantiomer injected) this method was not deemed suitable for the pharmacokinetic studies planned, since the therapeutic plasma concentration range of propafenone is 64-1044 ng/mL. The second chiral derivatizing reagent, 2,3,4,6-tetra-0-acetyl-β-D-glucopyranosylisothiocyanate (GITC), was synthesized in our laboratory. This reagent gave better resolution of the enantiomers (RS=1.4) within 15 minutes with enhanced sensitivity for detection (150 ng of each enantiomer injected). To further optimize the limit of detection for future pharmacokinetic studies of propafenone, R(-)-1 -(naphthyl) ethylisocyanate, a chiral derivatizing agent, was employed. This reagent reacted with racemic propafenone and permitted the resolution of both enantiomers within 24 minutes (R5=l.25) and the minimum level of detection was 100 ng (at the detector) for each enantiomer of propafenone. Using this method, linearity was established over the concentration range, 125-1000 ng for each enantiomer (injected) with a coefficient of determination (r²) of greater than 0.99. Reproducibility and precision of this assay method was obtained with an average coefficient of variability of 4.5% for the R(-) enantiomer and 7.2% for S(+) enantiomer at concentrations of 125-1000 ng/mL. Below the lower quantity, the NEIC-propafenone reaction virtually stopped at the conditions set for derivatization. A similar lack of reactivity at low concentrations was also observed with the GITC-propafenone reaction. The absence of an autocatalysing effect of propafenone at lower nanogram levels, as well as two possible conformational forms of propafenone were also investigated. The existence of two conformational isomers of propafenone, due to intramolecular hydrogen bonding in aprotic solvents, was chromatographically verified. In addition, chromatographic separation of all the proposed conformers was obtained, indicating that enantiomeric separation and quantitation of propafenone enantiomers as their urea derivatives is substantially hindered. To eliminate hydrogen bonding interactions, the carbonyl group of propafenone was blocked with dansylhydrazine and subsequently derivatized with the chiral R(-)NEIC reagent. The HPLC resolution (RS=1.35) of this dual derivative was better than that using the R(-) NEIC reagent alone, and the minimum level of detection was 2.5 ng for each enantiomer. Unfortunately, this procedure still did not provide adequate assay precision and accuracy at the lower levels required for single dose pharmacokinetic studies. / Pharmaceutical Sciences, Faculty of / Graduate

<p> This report covers two topics. First is the development of computer programs to carry out the calculations needed to determine the control policy to bring a process from one set of steady state conditions to another. Examples of the implementation of control policies for a liquid-liquid extraction column are included. Suggestions have been made for means of decreasing the calculation time and for means of increasing the size of problem that may be solved. </p> <p> The second part discusses an initial project of using a Supernova computer as a direct control computer. Characteristics of direct digital control are illustrated using an analog simulation of the extraction unit as the controlled process. </p> / Thesis / Master of Engineering (MEngr)

No description available.

With many processing advantages, electrophoretic deposition (EPD) has been chosen as the fabrication technique for inorganic-organic nanocomposites. However, before the EPD process, avoiding the particles agglomeration is considered a necessary perquisite for the success of fabrication. In this research, two different liquid-liquid extraction methods, one is one-step and the other is two-step, were developed to solve the agglomeration problem of inorganic particles. The adsorption mechanisms of the extractors and extraction mechanisms were investigated during this work. The strong adsorptions provided by –OH groups of the extractors and further Schiff base reaction allowed for the process of extraction. In the fabrication, polyelectrolytes acted as the film forming and charging agents. Relatively stable suspensions with extracted inorganic particles were prepared for the EPD of inorganic-organic nanocomposites. The thickness of deposited films is proportional to the concentration of the suspension and deposition time. With the addition of flame retardant inorganic particles, the prepared nanocomposite films showed an enhanced flame retardant performance. / Thesis / Master of Applied Science (MASc)

Master of Science

Digitized by Kansas State University Libraries

This thesis presents a study of colloidal particles dispersed in thermotropic liquid crystals. It has a specific focus on colloids in the presence of an interface between the liquid crystal and an isotropic fluid. Three systems are studied: colloids trapped at a planar interface between a cholesteric liquid crystal (CLC) and an isotropic oil, nematic emulsions with interfacial colloids and the influence of colloids on the phase transition kinetics of the cholesteric blue phase. Experiments are carried out using polarising optical and confocal microscopy. By combining these techniques, the director field of the liquid crystals could be imaged in combination with precise observation of the colloid locations. Custom image analysis algorithms are developed to extract the information. In the first system, we create an interface between a cholesteric liquid crystal and an isotropic liquid. Homeotropic anchoring leads to a well aligned cholesteric layer and the formation of the fingerprint texture. Fluorescent colloidal particles with planar surface anchoring are dispersed in the CLC. A majority of these particles decorate the interface. The final distribution of particles perpendicular to the interface has a clear dependence on the particle size. In the plane of the interface, surface defects form a template for the colloids. The second system is a particle dispersion within a short pitch CLC which exhibits a blue phase. The colloidal particles and associated defects act as nucleation sites for the blue phase in the cholesteric to blue phase transition. Colloidal particles cause localised melting from the blue phase to the isotropic phase and lead to a larger temperature range for coexistence between isotropic and blue phases. Furthermore, the isotropic regions can be faceted, their shape and size is controlled by the blue phase elasticity. In the final system, a nematic emulsion is created. Droplets of nematic LC are dispersed in water. Colloidal particles initially mixed into the liquid crystal decorate the interface between the two fluids. The addition of a surfactant switches the liquid crystal alignment at the fluid-fluid interface from planar to homeotropic. This forces a change in defect structure, from two boojums at the poles to a hedgehog defect in the droplet centre. The presence of colloids affects the switching dynamics and alters the final liquid crystal alignment preventing the droplets from forming a central radial defect. There is a symbiotic relationship between the particle properties - size and anchoring at the surface - and the elastic properties of the liquid crystal in the bulk and in the presence of an interface with an isotropic fluid. How the systems respond when the balance of these factors is altered is explored throughout the thesis.

The physical and chemical nature of chemically bonded phases used in high performance liquid chromatography have been studied. These bonded phases were characterized by a variety of chromotographic and non-chromatographic experiments. The non-chromatographic techniques included ¹³C NMR and batch extraction methods. The role played by the bonded phase as well as the mobile phase in determining the retention characteristics of the "stationary phase" were determined. The retention of solute molecules on bonded phases was found to be a function of the chain length of the bonded phase, the chemical nature of the bonded molecule, and the type of organic modifier used in the mobile phase. The energetics of the solute-stationary phase interactions was determined by the differential enthalpy and was found to be indicative of a partitioning process between two liquid phases. The retention process was also affected by the surface coverage of the bonded molecule. Optimum retention and separation characteristics were obtained with a hydrocarbon bonded phase of high surface coverage when used with a mobile phase containing a very polar organic modifier. The efficiency of these bonded phases was found to be independent of chain length as well as surface coverage of the bonded molecule. Some bonded phases which have specific functionalities incorporated into the bonded molecule are not true reversed phases. The selectivity of the bonded phases towards polar solute molecules was found to be affected by the type of organic modifier used in the mobile phase. The major accomplishment of this work shows that the stationary phase consists of the bonded molecule as well as trapped mobile phase. The composition of this ternary mixture is a function of the type and amount of bonded material and the type and amount of organic modifier used in the mobile phase.

No description available.