Thesis (MSc. (Chemistry)) -- University of Limpopo, 2013 / Drinkable water is water that is safe enough to be consumed by humans or used with low risk of immediate or long term harm. World-wide, insufficient access to portable water and use of sources contaminated with disease vectors, pathogens, and unacceptable levels of toxins is a huge problem. The use of such water for drinking and food preparation leads to the widespread of acute and chronic illnesses. This is a major cause of death and misery in many undeveloped countries. Reduction of waterborne diseases is a major public health goal in developing countries. Nanotechnology offers the possibility of an efficient removal of pollutants and microorganisms from water. Essentially, three classes of nanoscale materials were investigated as functional materials for water purification in this study. Silver nanoparticles, carbon nanotubes and beta ()-cyclodextrin polymers were synthesised and characterised specifically for purification of water samples. β-cyclodextrin is soluble in both water and other aqueous media. In order to render cyclodextrins insoluble, they were converted into highly cross-linked polymers, by polymerisation with a bifunctional linker, hexamethylene diisocyanate. Cyclodextrins were functionalised and synthesised with either the allyl or the benzoyl group. Characterisation with fourier transform infrared (FTIR) spectrophotometer confirmed the functionalisation process. Thereafter the scanning electron microscopy (SEM) analysis confirmed the polymers’ morphology to be spongy, and capable of absorbing contaminants. Multi-walled carbon nanotubes (MWCNTs) were treated with a mixture of sulphuric and nitric acid in order to introduce the carboxyl and hydroxyl groups. These were characterised by SEM, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR spectroscopy to confirm the functionalisation process. Silver nanoparticles were synthesised from sodium citrate and silver nitrate, using sodium dodecyl sulphate as a surfactant. Their characterisation was done by SEM, energy dispersive X ray (EDX) spectroscopy, TEM, UV/Vis spectroscopy and XRD to confirm a face centred cubic structure with an estimated crystallite size ranging from 50 to 100 nm.β-cyclodextrin polymers, functionalised multi-walled carbon nanotubes and silver nanoparticle-doped MWCNTs/cyclodextrin composites were characterised by SEM, TEM, XRD, Brunauer-Emmet-Teller (BET) and EDX. Analysis of the phenolic compound, 4-hydroxynitrobenzene in water, using these nanocomposites, demonstrated good capabilities of removing organic contaminants from water samples as indicated by their high absorption efficiencies of the contaminants. The synthesised metal-organic composites were tested for their effectiveness in removing organic contaminants as well as for eliminating Escherichia coli bacteria from water. The synthesised composites presented up to 97% absorption efficiency of organic contaminants and up to 100% inactivation of the bacteria. There was complete destruction of bacteria from the water analysed at various times and varying concentrations. After a long exposure of the nanocomposites to E. coli, pits were noticeable on the external morphology of the bacteria, thus suggesting that the nanocomposites are bactericidal. The bacterial activity increased with temperature,when studied between 10 oC and 30 oC.

Poly (lactic acid) (PLA) is a promising substitute for conventional petroleum-based polymer materials as a result of its environmentally benign quality and suitable physical properties. However, there are also problems associated with properties, such as brittleness, low heat deflection temperature, low melt viscosity, as well as cost that prevent wide-range applications of PLA This work reports on melt extrusion preparation of PLA/clay/wood nanocomposites involving various compatibilizers, resulting in remarkable improvements in mechanical as well as in thermal material properties. In particular, the tensile and flexural moduli of PLA/clay/wood nanocomposites with 30 wt. % wood flour and 5 wt. % nanoclay respectively increased from 3.75 to 7.08 GPa and from 3.83 to 6.01 GPa compared to neat PLA. The thermal decomposition temperature improved by about 10°C compared to that of PLA/wood composites A mathematical model was developed based on Eshelby's equivalent inclusion method and Mori-Tanaka's background analysis to successfully predict longitudinal elastic moduli of complex structured nanocomposite materials / acase@tulane.edu

A high-flow (10 L/min) nanoparticle respiratory deposition (NRD) sampler was designed and evaluated to facilitate lower limits of quantification (LOQ) for metal nanoparticles than a low-flow (2.5 L/min) version. The high-flow NRD consists of an inlet, impactor stage, diffusion stage, and a final filter. For the impactor stage, three nozzle sections each containing 12 nozzles were designed from theory to achieve a cut-off diameter (d50) of 300 nm. Various depths of 37-mm-diameter foam cylinders were tested for the diffusion stage to obtain a collection efficiency curve similar to the deposition of nanoparticles in the human respiratory tract, the nanoparticulate matter (NPM) criterion. The objective for the final filter was a collection efficiency of near 100% with minimal pressure drop. The collection efficiencies by size and pressure drop were measured for all components. The impactor stage with one of the nozzle plates had a d50 of 305 nm. The collection efficiency for the foam with a depth of 7 cm adjusted for presence of the impactor was the closest match to the NPM curve with a R2 value of 0.96. Chemical analysis of the metal content for foam media affirmed that the high-flow NRD would require less sampling time to meet LOQs than the 2.5 L/min NRD. The final filter with a modified support pad had a collection efficiency near 100%. The overall pressure drop of the sampler 4.4 kPa (17.5 in. H2O) limits its ability to operate with available belt-mounted personal sampling pumps, although modifications to the sampler design could eliminate this constraint.

A spectre is haunting contemporary technoculture: the spectre of Singularity. Ten years into a century thus far characterized chiefly by the catastrophic failure of global economic and political systems, deepening ecological anxieties, and slow-motion social crisis, the only sector of our collective cultural myth of Progress still vibrantly intact is the technological - a project which, in vivid contrast to the systemic failure that seemingly prevails at nearly every other level, continues to charge forward at breakneck speed. Since the late twentieth century, prompted by the all-but-exponential growth of machine intelligence and global information networks, and by the still largely obscure but increasingly profound-seeming implications of emerging nanotechnology, futurists and fabulists alike have postulated an imminent historical threshold whereupon the nature of human existence will be radically and irrevocably transformed in a sudden explosion of technological development. This moment of transcendence, it is supposed, is at most only a few years off; indeed, some say, it may have already begun. The "Singularity" - a term coined in 1986 by the mathematician and science fiction writer Vernor Vinge, and subsequently adopted throughout technocultural discourse - is at present the primary site of interpenetration between technoscientific and science-fictional figurations of the future, an area in which the longstanding binary distinctions between science and SF, and between present and future, are rapidly dissolving. As much as the Singularity thesis implies a total reorganization of society and of the self - which posthumanist cultural studies and cyborg theory have already begun mapping - it also poses a daunting existential challenge to the enterprise of SF itself, to the extent that the Singularity imposes what Vinge has described as "an opaque wall across the future," an impenetrable cognitive obstacle beyond which the extrapolative imagination cannot glimpse. For a genre long defined by its efforts to assert, through the narrative technique of extrapolation, a meaningful continuity between present and future, the Singularity presents a thorny problem indeed, demanding both a reevaluation of SF's conception of and orientation toward the future, and a new narrative model capable of grappling with the alien and often paradoxical complexity of the postsingular. This study is an inquiry into the properties and problematics of Singularity across fictional and nonfictional discourses, and as such it operates on two levels. Reading Singularitarian literature against a broadly articulated context of fringe-science and transhumanist movements, consumer culture, political and economic theory, and related areas of contemporary cyber- and technoculture, I examine how the metaphor of Singularity structures and signifies the aspirations and anxieties of late-twentieth and early twenty-first century technocivilization. As a project of literary criticism specifically, the study works to identify and theorize a grouping of texts that is emerging from cyberpunk and postcyberpunk tendencies in contemporary SF, organized around the premises of Singularity and the posthuman, and classifiable primarily in terms of an attempt to mount a response to the formal and conceptual problems Vinge has identified. Primary readings are drawn from a wide-ranging selection of twentieth- and twenty-first-century technocultural fiction, with emphasis on SF works by Charles Stross, Cory Doctorow, Neal Stephenson, Bruce Sterling, Rudy Rucker, and William Gibson.

Composite magneto-dielectric materials have been investigated over the years because of their potential applications in RF and microwave devices as the dielectric constant and permeability can be individually changed in these materials. In the recent past, there is a renewed interest in systems classified as ferroelectromagnets or multiferroics, which possess simultaneous ferroelectric and magnetic ordering as well as interesting magnetoelastic phenomena. In all these ferrite-ferroelectric materials, the coupling between the permeability (μ) of the magnetically ordered phase and permittivity (e) of the ferroelectric phase make them attractive candidates for multifunctional applications. Ba0.5Sr0.5TiO3 (BSTO) is a ferroelectric with potential applications in tunable filters, antennas, and thin film capacitors. BaFe12O19 (BaF) is a hard ferromagnet with large in-plane anisotropy which makes it promising for use in microwave and RF devices that need permanent magnets for biasing requirements. We have used magnetron sputtering to deposit multilayer films of BSTO and BaF on Al2O3 and heated Si/SiO2. To our knowledge this is the first attempt at combining these technologically important materials in multilayer form. The as-deposited films were amorphous and post-annealing was optimized until distinct BSTO and BaF x-ray peaks could be identified. Surface and images were obtained by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The multilayer structure and BSTO/BaF interfaces were identified using cross-sectional SEM. Magnetic properties of the multilayer films were measured using a Physical Properties Measurement System (PPMS) by Quantum Design at 10K and 300K over a range of magnetic field (0 < H < 7T). We have attempted to correlate some of the magnetic characteristics with the film microstructure. In addition, we have deposited layers of Fe3O4 nanoparticles onto both bare Si/SiO2 substrates and the surfaces of the multilayers using Langmuir-Blodgett technique. Preliminary images of monolayer Fe3O4 particles reveal some ordering present. We have also used the PPMS to look at the magnetic properties of the particles, both by themselves and deposited onto the multilayers to see what magnetic effects the particles have on ferrite-ferroelectric systems.

Philosophiae Doctor - PhD / The field of nanotechnology continues to offer solutions for biotechnologists whose target is to improve the quality of life by finding new therapies to combat diseases. Gold nanoparticles (AuNPs) have been showing great potentials in many biomedical applications. The antibacterial activity of the AuNPs presents a therapeutic option for conditions caused by bacterial infections such as chronic wounds. Also, these versatile particles can offer solutions in the treatments of infectious diseases and can also be exploited as “smart” vehicles to carry drugs, such as antibiotics, for improved efficiency. Moreover, the anti-inflammatory activity of AuNPs makes them useful in the management of prolonged inflammation caused by bacterial infections. The synthesis of AuNPs can be achieved by variety of physical and chemical methods that have been successfully applied in labs and industry. Nonetheless, the drawbacks of these “conventional” methods in terms of high cost, adverse health side effects and incompatibility with the ecosystem cannot be overlooked. Thus, new safer and more cost-effective protocols have been reported for the synthesis of AuNPs. Plants have provided alternate synthesis methods in which the reducing capabilities of the phytochemicals, found in the aqueous plant extracts, can be used to chemically synthesize AuNPs from gold precursors. The biosynthesis and characterization of AuNPs from the phytochemicals of several South African plants is investigated in this study. The study also reports the optimization of the AuNPs biosynthesis by varying reaction conditions such as temperature and plant extracts’ concentrations. Furthermore, the study highlights the wound healing activity of the AuNPs synthesized from selected plants by investigating their antibacterial activity on bacterial strains known to cause chronic wounds. The ability of these AuNPs to carry ampicillin in order to enhance the antibacterial activity is also described herein. The cytotoxicity of the biosynthesized AuNPs was evaluated on human normal fibroblasts cells (KMST-6). Additionally, the immunomodulatory effect of the biosynthesized AuNPs on the cytokines production from macrophages and Natural Killer (NK) cells was examined. The study was successful to produce biocompatible and safe AuNPs synthesized from the tested aqueous plant extracts. The resulted AuNPs showed different physicochemical properties by varying the reaction conditions. The AuNPs exhibited antibacterial activity against several Gram-positive and Gram-negative bacteria. Also, ampicillin was successfully loaded on the biosynthesized AuNPs, which led to the formation of more antibacterial active conjugated AuNPs compared to the free AuNPs. The green synthesized AuNPs were also found to have anti-inflammatory responses as shown by the reduction of pro-inflammatory cytokines from immune cells. In vitro assays showed that the biogenic AuNPs were not toxic to KMST-6 cells. Overall, the data suggest that plant extracts produce biologically safe AuNPs with antibacterial and anti-inflammatory activities that can be exploited in the treatment of chronic wounds and in the management of chronic inflammation.

>Magister Scientiae - MSc / Introduction: Together with bonding to both enamel and dentine, an ideal restorative material would display physical properties similar to that of natural tooth tissue and would not be prone to degradation as a result of the oral environment. This includes changes in colour. Glass ionomer technology has undergone many changes to its original chemistry since it was developed in the early 1970’s. In 1988 resin-modified glass ionomers were introduced and in 2008, nano-ionomers were introduced. As a result of the progression in material sciences and the use of more sophisticated techniques and methods in restorative dentistry, it is possible to accomplish much improved aesthetics and functional durability of a restoration, both anteriorly and posteriorly. However, for as long as aesthetic restorations have been available, and in spite of advances in material structure and performance, one of the greatest challenges facing clinicians still remains that aesthetic restorations have to be replaced relatively frequently as staining and discolouration is a common problem. Aim of the study: The aim of this study was to determine the stainability of four resin-modified glass ionomers and one glass ionomer cement when exposed to a staining broth. Objectives: To record any change in colour before and after exposing the sample with the staining broth using a spectrophotometer, to compare the stainability, to examine the depth of staining using a light microscope and to observe the particle size of the powder and the surface texture using Scanning Electron Microscopy of the four resin- modified glass ionomer cements and one glass ionomer cement. Materials and Methods: Four resin-modified glass ionomers (one nano-ionomer) and one glass ionomer (zinc-reinforced ionomer) were selected. All were shade A2, except for Vitremer™ which was not available in A2. 15 discs of each material were prepared. The discs were 15 mm in diameter and 2 mm in thickness. All the materials were handled and cured according to the manufacturers’ instructions. After curing, only one side of each disc was polished using Sof-Lex™ discs (3M ESPE, USA). The unpolished side of each disc was designated as a matrix finish. The specimens were all immersed in distilled water at 37 °C for one week. They were then immersed in a staining broth for a period of one week and readings were taken after a period of 2 hours, 4 hours, 8 hours, 24 hours and one week. Colour was read on each side of each disc at the indicated intervals with a spectrophotometer. The colour difference was calculated using the CIELAB colour co-ordinates. Sample discs were then sectioned to determine the depth of staining. An additional sample disc of each material was made for observation with the SEM and was therefore not stained. Also, an unmixed sample of each material was prepared for examination with the SEM. Results: In general, for all materials there was an increase in staining when assessed with the colour difference between the baseline colour and the 7 day reading. Ketac™ N100, showed the highest total colour change of 43.84 for the unpolished surface followed by Riva™ which showed the total colour change of 28.55 for the unpolished surface. This was similar to Fuji II LC® which had a total colour change of 28.16 for the unpolished surface. For Vitremer™, the total colour change increased to 18.07 for the unpolished surface. For the unpolished surfaces, ChemFil™ Rock showed the least colour difference from baseline to 7 days (ΔE*ab = 10.45), followed by Vitremer™ (ΔE*ab = 18.07). Both Fuji II LC® and Riva™ Light Cure showed similar colour change from baseline to 7 days for unpolished surfaces (ΔE*ab of 28.16 and 28.55 respectively). Ketac™ N100 showed the highest staining after 7 days in the staining broth with a colour difference of 43.84. For the polished surfaces, the colour change for Fuji II LC® was 25.72 which was similar to Riva™ Light Cure which was 22.44 and Ketac™ N100 which showed a colour change of 22.79 on the polished surface. ChemFil™ Rock showed the least colour change of 17.69 for the polished surface followed by Vitremer™ which showed a colour change of 23.63 for the polished surface. Thus, for both the unpolished and polished surfaces there was a similar staining pattern. Conclusion: In this study it was demonstrated that all products evaluated in this study showed some degree of staining when exposed to a staining broth when evaluated using the ΔE*ab CIELAB colour evaluation. Ketac™ N100 showed the highest colour change compared to the other materials, but the reason for this was not explored. Both Vitremer™ and ChemFil™ Rock showed similar patterns of staining. / 2020-09-01

Modern computing and mobile device technologies are now based on semiconductor technology with nanoscale components, i.e., nanoelectronics, and are used in an increasing variety of consumer, scientific, and space-based applications. This rise to global prevalence has been accompanied by a similarly precipitous rise in fabrication cost, toxicity, and technicality; and the vast majority of modern nanotechnology cannot be repaired in whole or in part. In combination with looming scaling limits, it is clear that there is a critical need for fabrication technologies that rely upon clean, inexpensive, and portable means; and the ideal nanoelectronics manufacturing facility would harness micro- and nanoscale fabrication and self-assembly techniques. The field of molecular electronics has promised for the past two decades to fill fundamental gaps in modern, silicon-based, micro- and nanoelectronics; yet molecular electronic devices, in turn, have suffered from problems of size, dispersion and reproducibility. In parallel, advances in DNA nanotechnology over the past several decades have allowed for the design and assembly of nanoscale architectures with single-molecule precision, and indeed have been used as a basis for heteromaterial scaffolds, mechanically-active delivery mechanisms, and network assembly. The field has, however, suffered for lack of meaningful modularity in function: few designs to date interact with their surroundings in more than a mechanical manner. As a material, DNA offers the promise of nanometer resolution, self-assembly, linear shape, and connectivity into branched architectures; while its biological origin offers information storage, enzyme-compatibility and the promise of biologically-inspired fabrication through synthetic biological means. Recent advances in DNA chemistry have isolated and characterized an orthogonal DNA base pair using standard nucleobases: by bridging the gap between mismatched cytosine nucleotides, silver(I) ions can be selectively incorporated into the DNA helix with atomic resolution. The goal of this thesis is to explore how this approach to “metallize” DNA can be combined with structural DNA nanotechnology as a step toward creating electronically-functional DNA networks. This work begins with a survey of applications for such a transformative technology, including nanoelectronic component fabrication for low-resource and space-based applications. We then investigate the assembly of linear Ag+-functionalized DNA species using biochemical and structural analyses to gain an understanding of the kinetics, yield, morphology, and behavior of this orthogonal DNA base pair. After establishing a protocol for high yield assembly in the presence of varying Ag+ functionalization, we investigate these linear DNA species using electrical means. First a method of coupling orthogonal DNA to single-walled carbon nanotubes (SWCNTs) is explored for self-assembly into nanopatterned transistor devices. Then we carry out scanning tunneling microscope (STM) break junction experiments on short polycytosine, polycationic DNA duplexes and find increased molecular conductance of at least an order of magnitude relative to the most conductive DNA analog. With an understanding of linear species from both a biochemical and nanoelectronic perspective, we investigate the assembly of nonlinear Ag+-functionalized DNA species. Using rational design principles gathered from the analysis of linear species, a de novo mathematical framework for understanding generalized DNA networks is developed. This provides the basis for a computational model built in Matlab that is able to design DNA networks and nanostructures using arbitrary base parity. In this way, DNA nanostructures are able to be designed using the dC:Ag+:dC base pair, as well as any similar nucleobase or DNA-inspired system (dT:Hg2+:dT, rA:rU, G4, XNA, LNA, PNA, etc.). With this foundation, three general classes of DNA tiles are designed with embedded nanowire elements: single crossover Holliday junction (HJ) tiles, T-junction (TJ) units, and double crossover (DX) tile pairs and structures. A library of orthogonal chemistry DNA nanotechnology is described, and future applications to nanomaterials and circuit architectures are discussed.

The discovery of ferroelectricity at the nanoscale has incited a lot of interest in perovskite ferroelectrics not only for their potential in device application but also for their potential to expand fundamental understanding of complex phenomena at very small size scales. Unfortunately, not much is known about the dynamics of ferroelectrics at this scale. Many of the widely held theories for ferroelectric materials are based on bulk dynamics which break down when applied to smaller scales. In an effort to increase understanding of nanoscale ferroelectric materials we use atomistic resolution computational simulations to investigate the dynamics of polar perovskites. Within the framework of a well validated effective Hamiltonian model we are able to accurately predict many of the properties of ferroelectric materials at the nanoscale including the response of the soft mode to mechanical boundary conditions and the polarization reversal dynamics of ferroelectric nanowires. Given that the focus of our study is the dynamics of ferroelectric perovskites we begin by developing an effective Hamiltonian based model that could simultaneously describe both static and dynamic properties of such materials. Our study reveals that for ferroelectric perovskites that undergo a sequence of phase transitions, such as BaTiO3. for example, the minimal parameter effective Hamiltonian model is unable to reproduce both static and dynamical properties simultaneously. Nevertheless we developed two sets of parameters that accurately describes the static properties and dynamic properties of BaTiO3 independently. By creating a tool that accurately models the dynamical properties of perovskite ferroelectrics we are able to investigate the frequencies of the soft modes in the perovskite crystal. The lowest energy transverse optical soft modes in perovskite ferroelectrics are known to be cause of the ferroelectric phase transition in these materials and affect a number of electrical properties. The performance of a ferroelectric device is therefore directly influenced by the dynamics of the soft mode. Interestingly, however, little study has been done on the effect of mechanical boundary conditions on the soft modes of perovskites. Understanding the effect of mechanical forces on the soft modes is critical to device applications as complicated growth structures often are the cause of pressures, stresses and strains. Using classical molecular dynamics we study the effect of hydrostatic pressure, uniaxial stress, biaxial stress and biaxial strain on the soft modes of the ferroelectric PbTiO3. The results of this study indicate the existence of Curie-Weiss laws for not only hydrostatic pressure, which is well known, but also for uniaxial stress, biaxial stress and biaxial strain. The mode frequencies are also seen to respond very differently to these mechanical forces and lead to a more complete picture of the behavior of nanoscale ferroelectrics. One nanoscale geometry of perovskite ferroelectrics is the pseudo one-dimensional nanowire. These structures have very unique properties that are highly attractive for use as interconnects, nanoscale sensors or more directly in computer memory devices. Perovskite nanowires have only recently been synthesized and the techniques are not well developed. While progress has been made towards consistently fabricating uniform, high quality nanowires experimental investigation of their properties is prohibitively difficult. Of immediate interest is the polarization reversal dynamics of ferroelectric nanowires. The reading and writing of bits of information stored in a wire's polarization state is done by switching the polarization. Again using classical molecular dynamics we study the polarization reversal dynamics in ferroelectric nanowires made of Pb(Ti1-xZrx)O3 disordered alloy. We find that there are two competing mechanisms for polarization reversal and that the interplay of these mechanisms is dependent on electric field strength. The dynamics in nanowires also sheds light on long standing theories about polarization reversal mechanisms in thin film and bulk geometries.

This thesis investigates the defects, charge states and spin properties of phosphorus doped silicon, and is motivated by a number of proposals for quantum information processing (QIP) that involve using the spin or charge of individual donors in silicon as qubits. The implantation of phosphorus into silicon is investigated; specifically the ability to remove damage and activate the implanted donors. The impact of implantation on the transport properties of silicon MOSFETs at cryogenic temperatures is used to investigate the damage. Implanting phosphorus into the MOSFET channel leads to reduced electron mobility. The defect density increases linearly with implant density (??ndefect = 0.08 ?? 0.01nimplant). Silicon implantation does not show this effect, suggesting that the additional defects are ionised P donors in the channel. Implant activation for low density donors was complete for an implant density of 2 x 1012 cm2. Similar studies were undertaken on devices with a variety of dielectrics. Thermally grown SiO2 was found to have the lowest defect density of those studied, although Al2O3 deposited via atomic layer deposition was found to have properties that may be useful for the fabrication of devices with low thermal processing budgets. The as-grown defect density of the thermal silicon dioxide was found to be 2.1 ?? 0.3 x 1011 cm2. Ion implantation of nanoscale devices allowed the spin properties of a small number of phosphorus donors in silicon to be probed via electrically detected magnetic resonance. This allowed the detection of the spin resonance of as few as 100 spins. This represents an improvement in number detection of 4 orders of magnitude over previous EDMR studies of donors in silicon. EDMR was used to investigate the properties of P donors in isotopically purified 28Si . The material had a background doping level too high to detect small numbers of spins, however, the narrow linewidth of the phosphorus resonance confirm that the isotopic purity is greater than 0.999. A proof-of-principle demonstration of pulsed EDMR of ion-implanted donors in silicon is presented. The spin dependent transient that results from manipulating the donor spins via pulsed ESR is sensitive to as few as 104 donors, and is a required component for observation of spin Rabi oscillations by this technique.