Call number: LD2668 .T4 1955 G37 / Master of Science

<p>The objectives of this work were (i) to develop a new methodfor the preparation of thin cellulose model films, (ii) to usethese model films for swelling measurements and (iii) to relatethe swelling of fibers and films to the dry strength ofpaper.</p><p>In the new film preparation method, NMMO(N-methylmorpholine-N-oxide) was used to dissolve cellulose andDMSO (dimethyl sulfoxide) was added to control the viscosity ofthe cellulose solution. A dilute solution of the cellulose wasspin-coated onto a silicon oxide wafer and the cellulose filmthus prepared was then precipitated in deionised water. Asaturated layer of glyoxalated-polyacrylamide was used toanchor the film onto the silicon oxide wafer. This proceduregave films with thicknesses in the range of 20-270 nm. Thefilms were cleaned in deionised water and were found by ESCAanalysis and contact angle measurements (θ<20°)to be free from solvents. Solid state NMR measurements onfibers spun from NMMO also indicated that the model filmconsisted of about 50% crystalline material and that thecrystalline structure was of the cellulose II type.Determination of the molecular weight distribution of thecellulose surface material showed that the NMMO treatmentcaused only a minor breakdown of the cellulose chains and thatlow molecular mass oligomers of glucose were not created.</p><p>It was further shown that atomic force microscopy (AFM)measurements could be used to determine the thicknessof thecellulose films, in both the dry and wet states. The thicknesswas determined as the height difference between the top surfaceand the underlying silica wafer measured at a position where anincision had been made in the cellulose film. The cellulosesolutions were also directly spin-coated onto the crystal usedin the Quartz crystal microbalance (QCM-D), pre-treated withthe same type of anchoring polymer. With this application,these model surfaces were shown to be suitable for swellingmeasurements with the QCM-D. The extent of swelling and theswelling kinetics in the presence of electrolytes, such asNaCl, CaCl2 and Na2SO4, and at different pH were measured inthis way. The films were found to be very stable during thesemeasurements and the results were comparable to the swellingresults obtained for the corresponding pulps. The swelling ofboth fibers and films followed the general behavior ofpolyelectrolyte gels in the presence of electrolytes and was inaccordance with the Donnan equilibrium theory. The films havebeen shown to differ from fibers with regard to the absence ofa covalent interior network. This influences the evaluation ofthe deswelling effects measured on the model films. Theswelling effect seen with different electrolytes has also beenconsidered in relation to the tensile strength of paperprepared from a kraftliner-pulp. In this study, it was foundthat there was no direct relationship between the swelling ofthe fibers, measured as WRV, and the strength of the paper inthe presence of different electrolytes at pH 5.</p><p><b>KEYWORDS:</b>absorption, carboxymethyl cellulose,cellulose, cellulose fibers, dissolving pulps, donnanequilibrium, electrolytes, film, ion exchange, ionization,kinetics, liner boards, microscopy, spinning, surfaces,swelling, tensile strength, water, water retention value.</p>

The properties of photo-induced gratings in germania doped glass fibers were studied. Permanent phase gratings in a fiber core were fabricated by the mixing of two contra propagating waves. Experiments are described and results are presented which show that the strength of a photoinduced grating is strongly dependent on the writing power as well as the laser writing wavelength. A rigorous development of linear coupled mode theory for the contra propagation geometry is given and used to model the experimentally observed grating responses as a function of fine tuning frequency of probing light. Measurements have been done of the amplitude and phase response of the grating structure and compared with theoretical models of uniform and chirped gratings. The theoretically predicted negative group velocity dispersion in fiber grating was observed interferometrically and described in detail. The nonlinear coupled mode theory has been fully implemented in a computer program and some numerical results are given in the second part of this thesis. The dynamics of a pulse propagating in the fiber grating is simulated and the results show its dependence on pulse energy, frequency detuning, and the type of grating geometry. A limitation is found in the dispersion property of a constant amplitude fiber grating so that the pulse compression ratio and the width of a compressible pulse is strictly limited to ≅250 picoseconds.

Colon cancer is the second most common type of cancer in the United States. Its incidence is linked epidemiologically to high levels of bile acids in the feces. Bile acids have been implicated as promotors and cocarcinogens in the etiology of colon cancer and as comutagens and mutagens in bacteria. These observations suggest the hypothesis that bile acids may interact directly with DNA. Using agarose gel electrophoresis we showed that bile acids convert covalently closed circular plasmid DNA to the open circular form, indicating strand breakage. We next treated the single stranded circular DNA of phage M13 with bile acids and found that the transfection efficiency of this DNA declined up to a thousand-fold. The concentrations of bile acids used were of the same magnitude as the fecal bile acid concentrations found in colorectal cancer patients. This inactivation was largely prevented when the bile acids were pretreated with cellulose fiber.

No description available.

This thesis concerns polarization mode dispersion (PMD) in optical fiber communications. Specifically, we study fiber birefringence, PMD stochastic properties, PMD mitigation and the interaction of fiber birefringence and fiber nonlinearity. Fiber birefringence is the physical origin of polarization mode dispersion. Current models of birefringence in optical fibers assume that the birefringence vector varies randomly either in orientation with a fixed magnitude or simultaneously in both magnitude and direction. These models are applicable only to certain birefringence profiles. For a broader range of birefringence profiles, we propose and investigate four general models in which the stochastically varying amplitude is restricted to a limited range. In addition, mathematical algorithms are introduced for the numerical implementation of these models. To investigate polarization mode dispersion, we first apply these models to single mode fibers. In particular, two existing models and our four more general models are employed for the evolution of optical fiber birefringence with longitudinal distance to analyze, both theoretically and numerically, the behavior of the polarization mode dispersion. We find that while the probability distribution function of the differential group delay (DGD) varies along the fiber length as in existing models, the dependence of the mean DGD on fiber length differs noticeably from earlier predictions. Fiber spinning reduces polarization mode dispersion effects in optical fibers. Since relatively few studies have been performed of the dependence of the reduction factor on the strength of random background birefringence fluctuations, we here apply a general birefringence model to sinusoidal spun fibers. We find that while, as expected, the phase matching condition is not affected by random perturbations, the degree of PMD reduction as well as the probability distribution function of the DGD are both influenced by the random components of the birefringence. Together with other researchers, I have also examined a series of experimentally realizable procedures to compensate for PMD in optical fiber systems. This work demonstrates that a symmetric ordering of compensator elements combined with Taylor and Chebyshev approximations to the transfer matrix for the light polarization in optical fibers can significantly widen the compensation bandwidth. In the last part of the thesis, we applied the Manakov-PMD equation and a general model of fiber birefringence to investigate pulse distortion induced by the interaction of fiber birefringence and fiber nonlinearity. We find that the effect of nonlinearity on the pulse distortion differs markedly with the birefringence profile.

M.Ing. (Electrical and Electronic Engineering) / A distributed temperature fiber sensor based on the ratio of the Raman anti-Stokes to Rayleigh backscattered light components is studied. The aim of the study is to propose a method of quantifying the noise exhibited in the Rayleigh backscattered signal and further propose correlation coding techniques to reduce the noise in the Rayleigh and Raman backscattered signals. The noise in the Rayleigh backscattered signal is referred to as “interferometric noise”. When Rayleigh scattering along the length of an optical fiber occurs, some of the scattered light travels in a direction opposite to the direction of propagation, and is called backscattered light. When the coherence length of the optical source permits interactions between the Rayleigh backscattered light, there is a possibility for the interacting backscattered light, within a distance that is half the coherence length, to interfere with each other. Furthermore, when the sensing optical fiber is greater than the coherence length of the optical source, there will be several interference sections along the length of the sensing fiber causing the intensity of the Rayleigh backscattered light at the photo-detectors to vary randomly. The intensity variation gives the Rayleigh backscattered signal a jagged appearance indicating the presence of interferometric noise. The longer the coherence length of the optical sources, the larger the intensity variations in the backscattered light, that is, the more the interferometric noise exhibited. The more the interferometric noise in the Rayleigh backscattered signal, the poorer the temperature accuracy of the distributed temperature sensor based on the ratio of the Raman anti Stokes to Rayleigh backscattered components. To quantify the interferometric noise affecting the Rayleigh backscattered signal, a mathematical model based on well-known scattering and interferometry theories is developed. Using the developed mathematical noise model, noise powers of approximately -52dBm and -40dBm for coherence lengths of 4m and 24m are respectively obtained...

Over the past decade, heterogeneous photocatalysis have gained lots of interest and attention among the organic chemistry community due to its applicability as an alternative to its homogeneous counterpart. Heterogeneous catalysis offers the advantages of easy separation and reusability of the catalyst. Several studies showed that under optimized conditions, efficient and highly selective catalytic systems could be developed using supported metal/metal oxide nanoparticles. In this dissertation, we summarize the progress in the development of supported palladium nanoparticles for different types of organic reactions. Palladium-decorated TiO2 is a moisture, air-tolerant, and versatile catalyst. The direct excitation of Pd nanoparticles selectively isomerized the benzyl-substituted alkenes to phenyl-substituted alkenes (E-isomer) with complete conversion over Pd@TiO2 under H2-free conditions. Likewise, light excited Pd nanoparticles catalyzed Sonogashira coupling, a C-C coupling reaction between different aryl iodides and acetylenes under very mild conditions in short reaction times. On the other hand, UV irradiation of Pd@TiO2 in alcoholic solutions promotes alkenes hydrogenation at room temperature under Argon. Thus, The photocatalytic activity of Pd@TiO2 can be easily tuned by changing the irradiation wavelength. Nevertheless, some of these systems suffer from catalyst deactivation, one of the main challenges faced in heterogeneous catalysis that decreases the reusability potential of the materials. In order to overcome this problem, we developed an innovative method called “Catalytic Farming”. Our reactivation strategy is based on the crop rotation system used in agriculture. Thus, alternating different catalytic reactions using the same catalyst can reactivate the catalyst surface by restoring its oxidation states and extend the catalyst lifetime along with its selectivity and efficiency. In this work, the rotation strategy is illustrated by Sonogashira coupling –problem reaction that depletes the catalyst– and Ullmann homocoupling –plausible recovery reaction that restores the oxidation state of the catalyst (Pd@TiO2). The selection of the reactions in this approach is based on mechanistic studies that include the role of the solvent and evaluation of the palladium oxidation state after each reaction. In a more exploratory analysis, we successfully demonstrated that Pd nanoparticles could be supported in a wide range of materials, including inert ones such as nanodiamonds or glass fibers. The study of the action spectrum shows that direct excitation of the Pd nanoparticles is a requisite for Sonogashira coupling reactions. The main advantages of heterogeneous catalysis compared to its homogeneous counterpart are easy separation and reusability of the catalyst. Finally in order to facilitate catalyst separation from batch reaction and develop a suitable catalytic system for continuous flow chemistry, we employed glass fibers as catalyst support for a wide variety of thermal and photochemical organic reactions including C-C coupling, dehalogenation and cycloaddition. Different metal/metal oxide nanoparticles, namely Pd, Co, Cu, Au, and Ru were deposited on glass wool and fully characterized. As a proof of concept, Pd decorated glass fibers were employed in heterogeneous flow photocatalysis for Sonogashira coupling and reductive de-halogenation of aryl iodides.

Dissertation submitted to the Faculty of Health Sciences, University of the Witwatersrand , Johannesburg, in fulfillment of the requirements for the degree of Master of Science in Medicine, Johannesburg, 2011 / HIV-associated sensory neuropathy (HIV-SN) is a common complication of HIV infection and its treatment with dideoxynucleoside drugs such as stavudine. Pain is a symptom in about 75% of cases of HIV-SN. The aim of this study was to set up the intraepidermal nerve fibre density (IENFD) quantification technique in a South African Laboratory and then to use this technique to investigate whether the presence of pain in individuals with HIV-associated sensory neuropathy was associated with the dying back of epidermal nerve fibres at the site at which pain was experienced.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the Degree of Doctor of Philosophy. J o h a n n e s b u r g , 2 0 1 3. / Structured carbon nanomaterials have attracted considerable interest because of their unique structures and outstanding properties. Among other structured carbon nanomaterials, carbon nanofibers (CNFs) have been the subject of study for several decades with particular interest having been paid towards their synthesis and application. However, control over the size and shape of these materials still remains a challenge. Three main components necessary for the synthesis of CNFs are the catalyst or template, the carbon source and the source of energy/power. It has been noted that catalyst morphology and the carbon source plays an important role in controlling CNF growth and morphology. As such one of the main challenges is to produce the catalyst particles that would yield the desired CNF morphology. In this study, we investigated methods for controlling the size and morphology of CNFs by synthesizing Ni and Cu catalysts of particular morphology, while using C2H2 and trichloroethylene (TCE) as a carbon source for the synthesis of CNFs. A mixture of TCE/C2H2 was also employed as a carbon source for comparison. The catalysts and synthesized CNFs were characterized by different techniques such as TEM, XRD, TPR, TGA, Raman spectroscopy, IR spectroscopy, etc. The synthesis of Ni nanoparticles (NPs) was achieved by reduction of Ni(acetate)2 with hydrazine (35%). CNFs were synthesized by deposition of TCE, C2H2 and their mixtures using a chemical vapor deposition technique (CVD) in the temperature range 400-800 oC. N2 and CO2 were used as carrier gases. TEM analysis of the Ni particles as a function of time revealed that the Ni underwent a morphological change with time. Further, as the temperature of the reaction changed, so did the shape of the carbon materials. The shapes changed from structures showing bilateral growth at T = 400 oC to tripod-like structures and multipod-like structures at T = 450 oC and T = 500 oC respectively. Irregular shaped materials were observed at T > 500 oC. It was also found that when acetylene or an acetylene/trichloroethylene mixture was used at T = 450 oC, helical (> 80%) and linear fibers were produced respectively. It was also demonstrated that the flow rate of H2, N2 and CO2 had a dramatic influence on the morphology of CNFs. CO2/TCEwas found to produce linear fibers with controlled sizes at 800 oC. The results demonstrated that the formation of tripod CNFs only occurs in a very narrow parameter regime. Manoko S. Maubane The preheating of the TCE prior to its deposition over a Ni particle catalyst was achieved using a double stage CVD reactor. TCE was subjected to high temperatures prior to its deposition at low temperatures. Results showed that the decomposition temperature was the key parameter in the synthesis of CNFs. It was found that during the decomposition, TCE breaks down into different species/radicals which then adsorb onto the catalyst particle to give CNFs of different morphology. Raman studies revealed that the synthesized CNFs showed an increase in graphitic nature when the temperature in the first reactor of a two stage reactor was increased. Decomposition of C2H2 was also performed over Cu NPs, and Cu modified catalysts (Cu@SiO2 and Cu/SiO2) with different silica coatings at 300 oC. These catalysts were prepared by reduction of Cu(acac)2 with hydrazine (35%). TEM images revealed that coiled CNFs were only produced from Cu/SiO2 grown in the presence of H2 (> 90 %; d = 60-70 nm). IR spectra of all the CNFs indicated the presence of surface C=C, C=O, CH3 and CH2 moieties, and that the ratios of peak intensities of C=O/CHx and C=C/CHx species indicated the variable CNF surface that was produced by the gases and the Cu particles used. It was thus revealed that the CNFs produced by different Cu catalysts have different chemical and physical properties and that these properties correlate with catalyst particle size and the gas mixtures used. CuO and SrO modified Cu catalysts (with different Cu/Sr ratios) were also employed using the CVD method for the synthesis of CNFs at 300 oC. These catalysts were prepared by a coprecipitation method. The TEM images of the CNFs revealed a mixture of straight and coiled CNFs with a broad diameter distribution (50-400 nm) dependent on the Cu/Sr ratio of the catalyst used. IR and TGA analysis revealed that the chemical composition of the CNFs changed as the SrO content changed. The SrO content also affected the Cu particle size and influenced the morphology of the Cu particles from which the CNFs grew.