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From introduction: The Fluorescence Excitation Spectrum or anthracene is known to vary considerably with the age and condition or the crystal. This thesis represents an attempt to improve the understanding of these variations. To put the problem on a quantitative basis it was found necessary to know both the ultraviolet reflection and absorption spectra. Reports of the reflection spectrum appear to have been confined to the case of polarised incident light. In addition the reflectivity measurements are always reported for a freshly cleaved surface. For these reasons the reflectivity of anthracene for various conditions of the reflecting surface was measured with unpolarised light. These varying reflectivities were used to further knowledge of the chemical processes at the crystal surface, as well as being used directly in the calculation of fluorescence excitation spectra. Reflection spectra with a- and b- crystallographic axis polarisations were also obtained. Since such spectra are reported in the literature it was possible, by comparison, to conclude that the experimental methods used in this thesis yielded valid results. The polarised measurements were used to obtain optical constants for the crystal. In the interests of readability most of the complicated process of converting the reflectivities to optical constants is dealt with in three appendices to the thesis.

The current world-wide interest in transdermal drug delivery makes the prospect of valid in vitro diffusion cell methodology highly attractive. A new laboratory diffusion cell has been designed and constructed based on theoretical principles and practical permeation reports surveyed in recent literature, and has been applied to the monitoring of betamethasone 17-valerate permeation. The cell performance has been validated with respect to hydrodynamic mixing efficiency and temperature of the receptor phase. The steady-state permeation of this corticosteroid has been monitored through various synthetic and animal membranes in order to select the most appropriate media for in vitro study. The permeation of betamethasone 17-valerate has been monitored from various types of commercial and extemporaneously prepared semisolid topical formulation (cream, lotion, ointment and scalp application), through silicone membrane, human and weanling pig stratum corneum, and full thickness hairless mouse skin, and these in vitro results have been compared to data from in vivo blanching assays, using the same formulations, in an attempt to correlate the findings. This experimental methodology has necessitated the development of ancillary analytical techniques. A column-switching high-performance liquid chromatographic method has been developed for the rapid on-line clean-up and analysis of betamethasone 17-valerate contained in the various topical formulations, which minimizes sample handling and extraction procedures. The method has been modified for the analysis of this corticosteroid in the isopropyl myristate receptor phase used in the in vitro permeation experiments, and scintillation counting of tritium-labelled water has been used to verify the integrity of the animal membranes. The comparison of in vitro permeation and in vivo blanching results indicate good correlation of the data in certain instances. The closest correlations have been observed when the human stratum corneum has been used in vitro and these results are compared to data from the occluded mode of the blanching assay. The results of the porcine and murine media have also correlated with the human in vivo data, whereas the silicone membrane appears applicable only in certain in vitro experiments. The results indicate that valid, comparative percutaneous absorption data may be obtained in vitro by using a well designed, validated diffusion cell system.

The rapidly growing interest in the potential use of topical drug delivery formulations has resulted in increased use of the skin as a vital port for drug delivery. Extensive research has been conducted in designing vehicles capable of delivering a desired amount of drug to a specific site, to produce the desired pharmacological response. Rooperol tetra-acetate is a lipophilic, cytotoxic drug with the potential for use in the treatment of solar keratosis. For effective pharmacological action, delivery of the drug to the epidermal/dermal junction of the skin is required. A study of the topical penetration properties of rooperol tetra-acetate from different topical bases, each possessing different physico-chemical properties, was performed. The assessment involved a comparison of the diffusion properties under occlusive and non occlusive conditions when the drug was formulated into a gel, Cetomacrogol Cream B.P. (oil-inwater), Simple Ointment B.P. and an extemporaneously prepared water-in-oil topical cream. The in vitro experiments were conducted using polydimethylsiloxane and rat membrane mounted in a Franz diffusion cell. The topical permeation kinetics of rooperol tetra-acetate were determined by exploring the release characteristics of the active ingredient from the vehicles formulated and the permeability properties of the drug through the membranes employed. Further studies involved investigating the utilization of supersaturated systems intended to increase the thermodynamic activity of the drug when formulated into a propylene glycol/water vehicle (with and without polymer). To measure the release of rooperol tetra-acetate into the skin from a topical base it was necessary to, firstly, develop a suitable quantitative method for the analysis of the active drug in the aqueous receptor phase of in vitro diffusion cells. The second stage of product development was the design of an effective delivery system to facilitate the release of the diffusant from its base. A high performance liquid chromatographic method was utilized for the identification and quantification of the active drug. As validation is an important aspect in the development and subsequent utilization of an analytical procedure, the developed HPLC technique was validated by determining the precision, accuracy, range, limit of quantitation and sensitivity of the system. Lastly, the stability of rooperol tetra-acetate at elevated temperatures was assessed and a stability profile of the drug was generated for the three-month period of analysis. The results obtained following chromatographic analysis of the receptor phase sampled during the diffusion experiments indicate that the gel and oil-in-water formulations most effectively promoted the diffusion of rooperol tetra-acetate across polydimethylsiloxane membrane. The water-in-oil system exhibited lower flux rates and the ointment showed the least drug release. Occlusion of the topical vehicle increased the diffusitivity of the permeant from all formulations analysed. The permeation assessment results of the supersaturated systems showed enhanced diffusion of rooperol tetra-acetate across polydimethylsiloxane and rat membrane. The high thermodynamic activity existing in supersaturated systems most effectively increased the driving force for drug diffusion resulting in enhanced percutaneous penetration of rooperol tetra-acetate beyond the release and transport limitations of saturated solutions. These results provide the basis on which an effective topical drug delivery vehicle may be designed for this new drug entity.

The potential of non-viable Azalia filiculaides for the removal of Cu and Ni from aqueous solutions and the possibility of scaling up existing lab scale Azalia column systems was investigated. The effects of factors such as metal starting concentration, pH and two metals in solution on the removal of Ni and Cu from aqueous solution by dried and crushed Azalia biomass were studied in batch systems. Aqueous solutions of Ni with starting concentrations between 1000 and 2000J.lmolll gave the most efficient Ni removal by Azalla biomass. For Cu the optimum starting concentration for adsorption was 50J.lmol/l. The adsorption capacity of both eu and Ni increased as the starting pH of the sorption media increased. The optimum pH for Ni adsorption was found at pH 7 and for Cu, at pH 5. - Awlla biomass had a higher. maximum binding capacity (qrnax) for Cu than for Ni at pH 5. The removal of both Cu allct Ni showed little or no variation with the presence another metal in solution. Kinetic studies show that both Cu and Ni adsorbed rapidly onto the Azalia biomass. The removal of Cu and Ni from aqueous solutions using non-viable Azalia biomass was investigated in a lab scale fixed-bed column and an upscaled 4L column system. The nonviable Azalla filiculaides biomass when dried and used in a column for adsorption of Cu and Ni showed good physical stability under many different conditions. Preparation of the biomass before it could be used in the columns was very simple and did not involve any significant pretreatment steps. Prolonged exposure to UV light decreases Azalia biomass capacity for Ni and Cu adsorption. Column adsorption of Cu and Ni from aqueous solutions was successfully upscaled approximately 100 times. Relative to the lab scale column, the 4L column performed better for the uptake of Cu and Ni per gram of biomass. The larger column was also able to operate at relatively higher flow rates. The biomass showed good reusability with little change in the amount of Ni adsorbed in 10 consecutive cycles. Electron micrographs showecf little or no change in the physical structure and integrity of the Azolla biomass after exposure to mineral acids, Ni solution and high flow rates over 10 consecutive adsorption and desorption cycles. As much as 80% Ni and 70 % Cu was recovered when desorption profiles were generated using O.lMHCI as a desorption agent. The 4L column system was also tested using a highly concen~rat:~ Ni plating bath solution.(Nicrolyte 1). Only 18 % of the Ni could be removed from the expended Nicrolyte 1 pla~Jng solution after treating only 25L, indicating that Azolla biomass is more suited for removal of metals from more dilute industrial effluents.

Knowledge of the absorption of inhalation anaesthetic agents is essential if one is to safely administer them. Despite many years of research in linear science, no model has been described that can reliably predict inhalation agent uptake. To date no published investigation has looked for non¬linearity in the absorption process. The aim if this research project was to determine if the absorption of anaesthetic agents is non-linear, using isoflurane and enflurane as examples. To detect non-linearity, four conditions must be met: <ul> <li>Sensitivity to initial conditions, </li> <li>Fractal Dimension of the attract or, </li> <li>Invariant probability distribution of the attractor, and</li> <li>Detection of an underlying dynamical process. <br></li></ul> Ten measured time series for both isoflurane and enflurane absorption were measured. These were then compared with ten noise signals, with similar standard deviations, means and number of points in the series. Calculated Lyapunov exponents tested sensitivity to initial conditions. The dimension of the attractor was calculated using the following statistics, each giving an approximation of the fractal dimension. Approximate entropy, information entropy, correlation dimension and fractal dimension (box counting method). The Invariant probability distribution of the attractor was tested for using non-linear forecasting. Detection of an underlying dynamical process was determined by the method of surrogate data. Each of the four conditions required have been met with statistical significance ( p< 0.05) and acceptable statistical power (>0.8). It is therefore concluded that the absorption of both isoflurane and enflurane are non-linear processes. The implications and implementations in anaesthesia practice are discussed. / Thesis (PhD (Anaesthesiology))--University of Pretoria, 2005. / Anaesthesiology / unrestricted

Gas absorption rates were experimentally determined for a number of tworphase gas-liquid systems in co-current horizontal flow through circular tubes. Sparingly soluble gases were used in order to determine the liquid phase resistance to mass transfer. A series of experiments was designed to separate the effects of gas density, liquid-phase diffusivity, viscosity, surface tension, and tube diameter, on the mass transfer rates. The gas-liquid systems employed, in a single tube 1.757 cm. in diameter, were CO₂-water, He-water, CO₂-ethanol, and CO₂-ethylene glycol. Two additional tube sizes, 1.228 and 2.504.cm. in diameter were employed with the C02-water system to determine the effect of tube diameter. The gas and liquid flow rates used produced four different flow regions, bubble, plug, slug, and annular flow. The gas, and liquid, superficial velocities ranged from 0.1 to 40 fps, and 0.5 to 3.6 fps, respectively. Two correlations were developed for predicting mass transfer rates in two-phase flow. The first, based on a theory that each bubble represents a "mixing stage", is applicable to the bubble and plug regions of flow, and correlates the experimental' data for a wide range of liquid physical properties, as well as gas and liquid flow rates, with a probable error of approximately 15%. The second correlation, applicable to slug flow, empirically correlates the data for this region, over the same wide range of physical properties and flow rates, with a probable error of approximately 10%. The surface renewal or "penetration theory" mechanism of transfer is shown to be consistent with the experimental results obtained in the bubble and plug regions. In the slug region, on the other hand, evidence is available to indicate that another mechanism (probably that proposed by Kishinevskii), becomes increasingly important as the degree of turbulence increases. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

The shape of the Ne.λ6074.3 A° absorption line profile has been investigated using the Zeeman scanning technique. Neon glow discharges at three pressures, 2 Torr, 50 Torr, and 100 Torr, were used as absorbers while a 2 Torr Geissler tube was used as the source. The self-pressure broadening of the observed line was clearly observed and the rate of broadening compares well with theoretical estimates made from the impact theory with a van der Waals interaction assumed. No shift was detected, in contradiction to the theory. This lack of shift, and the rate of pressure broadening observed, were in agreement with the results of Smith (14) regarding the shift and broadening of the Ca.λ6573 A° line by neon. / Science, Faculty of / Physics and Astronomy, Department of / Graduate