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Effects of pyrene on the photophysical and two-photon absorption-based nonlinear optical properties of indium (III) phthalocyanines

  • Authors: Sanusi, Kayode , Nyokong, Tebello
  • Date: 2014
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/189957 , vital:44951 , xlink:href="https://doi.org/10.1080/00958972.2014.959509"
  • Description: Photophysical and two-photon-dependent nonlinear absorption properties of two chloroindium(III) phthalocyanines bearing pyrene units have been investigated. The tetra- (3) and the tri- (4) pyrene-substituted phthalocyanines exhibit strong triplet absorption with high triplet yields ( ) of 0.79 and 0.83, respectively. The measured nonlinear optical data, such as the two photon absorption cross-sections, the third- and second-order nonlinearities were found to be comparable with those of literature, thus, making the compounds promising candidates for a broad range of nonlinear optical applications.
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  • Date Issued: 2014

Effects of pyrene on the photophysical and two-photon absorption-based nonlinear optical properties of indium(III) phthalocyanines

  • Authors: Sanusi, Kayode , Nyokong, Tebello
  • Date: 2014
  • Language: English
  • Type: Article
  • Identifier: vital:7314 , http://hdl.handle.net/10962/d1020540
  • Description: Photophysical and two-photon-dependent nonlinear absorption properties of two chloroindium(III) phthalocyanines bearing pyrene units have been investigated. The tetra- (3) and the tri- (4) pyrene-substituted phthalocyanines exhibit strong triplet absorption with high triplet yields () of 0.79 and 0.83, respectively. The measured nonlinear optical data, such as the two photon absorption cross-sections, the third- and second-order nonlinearities were found to be comparable with those of literature, thus, making the compounds promising candidates for a broad range of nonlinear optical applications. , Original publication is available at http://dx.doi.org/10.1080/00958972.2014.959509
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  • Date Issued: 2014

Effects of redox mediators on the catalytic activity of iron porphyrins towards oxygen reduction in acidic media

  • Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
  • Date: 2014
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
  • Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
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  • Date Issued: 2014

Efficacy of two medical plant extracts and metformin in the prevention of diet induced fatty liver

  • Authors: Tshidino, Shonisani Cathphonia
  • Date: 2014
  • Subjects: Plant Extracts -- Therapeutic use , Medicinal plants
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: http://hdl.handle.net/10948/9066 , vital:26461
  • Description: Non‐alcoholic fatty liver diseases (NAFLD) is manifested in the absent of alcohol abuse. This disease is the major cause of liver failure and death among adults and children worldwide, including South Africa. Its increasing prevalence urges the need of therapeutic intervention. The main objectives of this study were to investigate the following: (1) The effect of 38.9% high fat diet (HFD)‐induced insulin resistance and fatty liver in male Wistar rats, (2) The efficacy of aqueous extracts from Sutherlandia frutescens leaves and Prunus africana bark and metformin in the treatment of HFDinduced insulin resistance and fatty liver. Male Wistar rats were fed on HFD (the HF group) or normal rat chow (the LF group) for 12 weeks. Even though the HFD‐fed rats had developed insulin resistance by week 12, fatty liver developed by week 16. After week 12, the HF group was divided into four groups of 6‐7 rats each and three of those groups were gavaged with either 0.125 mg P. africana extract/kg bwt/day (the HF+Pa group) or 50 mg S. frutescens extract kg bwt/day (the HF+Sf group) or 16 mg metformin/ kg bwt/day (HF+Met group), while kept on the same diet for an additional of 4 weeks, to investigate whether two medicinal plant extracts and metformin can prevent HFD to induce fatty liver or not. After 16 weeks, the liver histological images revealed that the HF group developed fatty liver in the form of both microsteatosis and macrosteatosis. Fatty liver was confirmed by significant increased liver total lipid (TL) and activities of glucose‐6‐phosphate dehydrogenase (cG6PD) and xanthine oxidase (XO), mitochondrial NADH oxidase (mNOX) and by a decrease (P<0.05) in the activities of the homogenate superoxide dismutase (hSOD) and mitochondrial complex II in the HF group, when compared to the LF group. Since the activities of mCS and cACL enzymes were not changed in the HF group, hence increased cG6PD activity in the HF group indicates that there was increased NADPH demand for lipid accumulation from activated NEFAs taken up by the liver from circulation and for maintenance of the NADPH‐dependent antioxidants and oxidants, respectively. The obtained data also show that mitochondria of the HFD‐fed rats adapted to an increase in energy availability, thereby compensation through decreasing complex II activity, to allow electron flux from β‐oxidation to respiratory chain in the HF group. Liver TL content was significantly decreased in the rats treated with metformin and P. africana extract, but not in the rats treated with S. frutescens when compared to the HF group (P < 0.05). However, the TL content remained >5% per liver weight in all treated groups. The present study demonstrates that these two plant extracts and metformin have different glucogenic and lipogenic effects from that presented by HFD alone when compared to the LFD alone. In conclusion, metformin and P. africana extract can attenuate HFD‐induced fatty liver without changing the dietary habits. Hence S. frutescens extract is less effective in the prevention of HFD‐induced fatty liver. A change in the dietary habits is recommended to be considered during the use of these three remedies in the treatment of HFD‐induced insulin resistance and fatty liver. All three treatments enhanced antioxidant capacity, and may improve insulin resistance and fatty liver mediated by the present HFD through different mechanism of actions in the liver.
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  • Date Issued: 2014

Electing high-order modes in solid state laser resonators

  • Authors: Iheanetu, Kelachukwu
  • Date: 2014
  • Language: English
  • Type: Thesis , Masters , MSc (Physics)
  • Identifier: http://hdl.handle.net/10353/995 , vital:26516
  • Description: The first chapter considered the fundamental processes of laser operation: photon absorption, spontaneous and stimulated emissions. These processes are considered when designing a laser gain medium. A four-level laser scheme was also illustrated. Then, the basic components and operating principle of a simple laser system was presented using a diode end-pumped Nd:YAG solid state laser resonator. The second chapter considered laser light as light rays propagating in the resonator and extensively discussed the oscillating field in the laser resonators. It examined the characteristics of the fundamental Gaussian mode and the same theory was applied to higher-order modes. Chapter three started with an introduction to beam shaping and proceeded to present a review of some intra-cavity beam shaping techniques, the use of; graded phase mirrors, difractive elements { binary phase elements and spiral phase elements. Also, a brief discussion was given on the concept of conventional holography and digital holography. The phase-only spatial light modulator (SLM) was presented, which by default is used to perform (only) phase modulation of optical fields and how it can be use to perform amplitude modulation also. Finally, a detailed discussion of the digital laser which uses the intracavity SLM as a mode selection element was presented, since it was the technique used in the experiment. The elegance of dynamic on-demand mode selection that required only a change of the grey-scale hologram on the SLM was one quality that was exploited in using the digital laser. The next two chapters presented the experiments and results. The concept of the digital laser was first used in the experiment in chapter four, to assemble a stable diode endpumped Nd:YAG solid state laser resonator. Basically, the cavity was of hemispherical configuration using an intra-cavity SLM (virtual concave mirror) as a back re ector and a at mirror output coupler. A virtual concave mirror was achieve on the SLM by using phase modulation to generate the hologram of a lens, which when displayed on the SLM made it to mimic a concave mirror. Then the next phase was using symmetric Laguerre-Gaussian mode function, of zero azimuthal order to generate digital holograms that correspond to amplitude absorbing concentric rings. These holograms, combined with the hologram that iv mimics a concave mirror were used on the SLM to perform high-order Laguerre-Gaussian modes selection in the cavity. The fifth chapter presented the results of the mode selection and considered the purity of the beam at the output coupler by comparing measured modal properties with the theoretical prediction. The outcome confirmed that the modes were of high purity and quality which further implied that the cavity was indeed selecting single pure high-order modes. The results also demonstrated that forcing the cavity to oscillate at higher-order modes (p = 3) extracted 74% more power from the gain medium compared to the fundamental mode (p = 0), but this extra power is only accessible beyond a critical pump input power of 38.8 W. Laser brightness describes the potential of a laser beam to achieve high intensities while still maintaining a large Rayleigh range. It is a property that is dependent on beam power and its quality factor. To achieve high brightness one needs to generate a beam that extracts maximum power from the gain with good beam quality. Building on the experiments demonstrated in this study, one can make the correct choices of output coupler's re ectivity, the laser gain medium's length and doping concentration and the pump mode overlap for a particular mode to further enhance energy extraction from the cavity, and then using well known extra-cavity techniques to improve the output beams quality factor by transforming the high-order mode back to the fundamental mode. This will electively achieve higher laser brightness.
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  • Date Issued: 2014

Electrical conductivity experiments on carbon-rich Karoo shales and forward modelling of aeromagnetic data across the Beattie Anomaly

  • Authors: Branch, Thomas Cameron
  • Date: 2014
  • Subjects: Earth sciences -- South Africa -- Karoo , Geology -- South Africa -- Karoo
  • Language: English
  • Type: Thesis , Masters , MSc
  • Identifier: vital:10662 , http://hdl.handle.net/10948/d1014544
  • Description: The Beattie Magnetic Anomaly is the world’s longest terrestrial magnetic anomaly with a strike length of over 1000 km and a wavelength in excess of 100 km. Collinear with this is a large belt of elevated crustal conductivities called the Southern Cape Conductive Belt. Historical crustal interpretations proposed a common source of serpentinized ophiolite as an explanation for both the anomalous crustal magnetic susceptibility and electrical conductivities. Spreading between the Western and Eastern Cape of South Africa the mid- to lower crust that hosts these anomalies is obscured by the overlying Cape and Karoo Supergroups. Between 2003 and 2006, three high resolution geophysical experiments were completed across the surface maximum of the Beattie Magnetic Anomaly (BMA) and the Southern Cape Conductive Belt (SCCB). These included a magnetotelluric (MT) survey and near vertical reflection and wide angle refraction seismic profiles. Within the MT inversion model the SCCB appeared as a composite anomaly, which included a mid-crustal conductor which is spatially associated with the BMA and a laterally continuous upper crustal conductor which is located at depths equivalent to the lower Karoo Supergroup. Subsequently; the upper crustal conductor was identified in northern and eastern extensions of the magnetotelluric profile; a distance in excess of 400 km. Historical magnetometer and Schlumberger Sounding experiments have previously identified elevated conductivities in the Karoo sequences which were attributed to the Whitehill and Prince Albert formations. These carboniferous, transgressive sediments are known to be conductive from borehole conductivity surveys and direct measurements at surface. In order to constrain the conductive properties of these sediments, impedance spectroscopy (IS) experiments were completed on core samples collected from a historical borehole drilled near to the MT profile. Part One of this thesis presents the results of these experiments, which support the proposition that the Whitehill and Prince Albert Formations are responsible for the laterally continuous, sub-horizontal, upper crustal conductor visible in the MT inversion model. Vitrinite reflectance studies were performed on the same samples by the Montanuniversität, in Leoben, these results corroborate the proposition that elevated organic carbon, of meta-anthracite rank, is the primary conductive phase for the Whitehill and Prince Albert formations. Part two of this thesis completed forward modelling exercises using historical aeromagnetic data previously collected across the Beattie Magnetic Anomaly. Preliminary models were unable to fit the geometry of any single magnetic model with conductors present in the MT inversion model discounting the proposition that the SCCB and BMA arise from a single crustal unit. Two constrained models were arrived at through an iterative process that sought a best fit between the measured data and the NVR crustal interpretations. The first model, proposes a largely resistive unit which incorporates portions of elevated crustal conductivity; these conductors are spatially correlated to crustal portions also characterised by high seismic reflectivity. The size of this modelled body suggest the likely host of the BMA is an intermediate plutonic terrane, analogous with the Natal sector of the Namaqua Natal Mobile Belt as well as the Heimefrontfjella in Dronning Maud Land, Antarctica, with magnetite hosted within shear zones. This is in agreement with previous studies. The second model proposes a lower crustal sliver imaged in the NVR data at depths proximal to the Curie Isotherm for magnetite and hematite as the source of the BMA. At these depths geomagnetic properties such as burial magnetisation or thermo-viscous remanent magnetism (TVRM) can potentially be linked to regional scale tectonic processes and can theoretically elevate a body’s net magnetic susceptibility. TVRM has been proposed for long wavelength crustal anomalies elsewhere.
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  • Date Issued: 2014

Electrocatalytic behahiour of cobalt tetraamino-phthalocyanine in the presence of a composite of reduced graphene nanosheets and of multi-walled carbon nanotubes

  • Authors: Nyoni, Stephen , Nyokong, Tebello
  • Date: 2014
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/189784 , vital:44931 , xlink:href="https://doi.org/10.1016/j.electacta.2014.05.093"
  • Description: A composite of multi-walled carbon nanotubes (MWCNT) with reduced graphene nanosheets (rGNS-2) was developed in order to minimize the restacking of the latter. The composite was used to modify a glassy carbon electrode (GCE). GCE was further modified with cobalt tetraamino phthalocyanine (CoTAPc). The modified electrode is represented as rGNS-2-MWCNT-CoTAPc-GCE. X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electrochemical microscopy and Raman spectroscopy were used to explore into surface functionalities, morphology and topography of the nanocomposite. The rGNS-2-MWCNT-CoTAPc-GCE had a low limit of detection of 3.32 × 10−8 M towards the detection of paraguat as a test analyte. A mechanism for paraquat detection using an rGNS-2-MWCNT-CoTAPc-GCE is also proposed in this work.
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  • Date Issued: 2014

Electrochemical behaviour of gold nanoparticles and Co tetraaminophthalocyanine on glassy carbon electrode

  • Authors: Maringa, Audacity , Antunes, Edith M , Nyokong, Tebello
  • Date: 2014
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/241573 , vital:50951 , xlink:href="https://doi.org/10.1016/j.electacta.2013.12.132"
  • Description: We report on the electrodeposition of gold nanoparticles (AuNPs) onto the glassy carbon electrode (GCE) followed by polymerization of cobalt tetraamino phthalocyanine (CoPc(NH2)4) on top (represented as poly-CoPc(NH2)4-/AuNPs-GCE). The modified electrode where CoPc(NH2)4 is polymerized first followed by deposition of AuNPs is represented as AuNPs/poly-CoPc(NH2)4-GCE. In the absence of AuNPs, the electrode is represented as poly-CoPc(NH2)4-GCE or for AuNPs alone (AuNPs-GCE). The surface coverage was 1.5 × 10−9 mol cm−2 for AuNPs-GCE and 3.0 × 10−9 mol cm−2 for the rest of the modified electrodes. AuNPs/CoPc(NH2)4-GCE exhibited high electrocatalytic activity towards the oxidation of nitrite, with detection potential of 0.76 V. The catalytic rate constant of 3.96 × 107 cm3 mol−1 s−1 was obtained for nitrite oxidation.
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  • Date Issued: 2014

Electrochemical inclusion of catechol into singlewalled carbon nanotubes: application for sensors

  • Authors: Oni, Joshua , Limson, Janice
  • Date: 2014
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/431090 , vital:72743 , xlink:href="10.1109/BioCAS.2014.6981727"
  • Description: We report on the use of catechol for the electrochemical activation of acid-functionalised single-walled carbon nanotubes immobilised on glassy carbon electrodes. Following well-published methods for catechol activation of bare glassy carbon electrodes, these studies show the efficacy of extending the method to activation of carbon nanotubes. Voltammetric scans in catechol show an increase in current response of 37 μA for the catechol redox pair over a maximum of three cycles during the catechol activation step. An increase in the ease of electron flow is indicated by a larger value for K app , which corresponds to a decrease in R ct obtained during impedance measurements. Catechol activation enhanced electron transfer, potentially afforded by an ease of electron passage due to a decrease in the resistance of the layer.
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  • Date Issued: 2014

Electron microscopy characterisation of polycrystalline silicon carbide

  • Authors: Ndzane, Nolufefe Muriel
  • Date: 2014
  • Subjects: Electron microscopy , Silicon carbide
  • Language: English
  • Type: Thesis , Masters , MSc
  • Identifier: vital:10553 , http://hdl.handle.net/10948/d1020634
  • Description: This dissertation focuses on an electron microscopy investigation of the microstructure of SiC layers in TRISO coated particles deposited by chemical vapour deposition under different experimental conditions, which include temperature, concentration of gases and deposition time. The polycrystalline β-SiC was deposited from the decomposition of methyl trichlorosilane MTS in the presence of hydrogen (H2) as carrier gas. Scanning electron microscopy (SEM), using the backscattered electron (BSE) mode, was used to image the microstructure of and defects in the SiC layers of TRISO particles. Electron backscatter diffraction (EBSD) in the SEM was used to determine the SiC grain sizes and distribution thereof in TRISO particles deposited under different conditions. For samples with a poor EBSD indexing rate, transmission Kikuchi diffraction and transmission electron microscopy (TEM) investigations were also carried out. From the results, the effects of growth temperature on the SiC microstructure, specifically on the grain size and shape and the porosity were determined. The effects of cooling or non-cooling of the gas inlet nozzle on the SiC microstructure were also investigated. TEM and scanning TEM (STEM) analyses of the SiC layers in TRISO particles were performed to image the defects and reveal the crystallinity of SiC layers. The microstructure and composition of SiC tubes fabricated by reaction bonding (RB) was also investigated by using electron microscopy and Raman spectroscopy. SEM-BSE imaging of RBSiC samples allowed the identification of impurities and free silicon in the RBSiC. Finally, the penetration of the metallic fission product, palladium, in reaction bonded SiC at a temperature of a 1000ºC is determined. A brief comment on the suitability of RBSiC as candidate for fuel cladding in a PWR is made. A short discussion of the suitability of the characterisation techniques used is included at the end.
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  • Date Issued: 2014

Electronic Governance (E-Governance) as a Public Sector Management Tool for service provision in Buffalo City Metropolitan Municipality

  • Authors: Moyo, Thokozani P
  • Date: 2014
  • Language: English
  • Type: Thesis , Masters , MPA
  • Identifier: vital:11714 , http://hdl.handle.net/10353/d1015268
  • Description: The study explores the use of Electronic governance (E-governance) as a Public Sector management tool for service provision in the Buffalo City Metropolitan Municipality. The main research question being pursued sought to find out the extent to which E-governance can be an effective tool for public sector management and service provision in the municipality. The study used both quantitative data (obtained through questionnaire survey) and qualitative data (through in-depth responses from municipality employees). The findings of the study seem to indicate that electronic governance is being utilised by a lesser percentage of citizens although it seems to be slowly gaining popularity with the highly educated and younger members of the public. Some members of the communities were still adamant to using online resources for different reasons. The study also reveals some challenges such as poverty, inequality and illiteracy as some of the hindrances to e-government. However, there is a degree of success of electronic governance in the municipality as evidenced by the percentage of the population now using the online transactions. A lot needs to be done in order to view e-governance as a true success in this municipality of Buffalo City Metropolitan if services are to be delivered effectively and efficiently to the people. It is therefore strongly recommended that there is a need to put in place good educational measures to ensure that the citizens are informed about various ways of doing online transactions with the municipality other than physically going there.
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  • Date Issued: 2014

Electropolymerized Fluorinated Aniline-Based Fiber for Headspace Solid-Phase Microextraction and Gas Chromatographic Determination of Benzaldehyde in Injectable Pharmaceutical Formulations

  • Authors: Mohammadi, Ali , Mohammadi, Somayeh , Moghaddam, Bayandori A , Masoumi, Vahideh , Walker, Roderick B
  • Date: 2014
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/184120 , vital:44175 , xlink:href="https://doi.org/10.1093/chromsci/bmt152"
  • Description: In this study, a simple method was developed and validated to detect trace levels of benzaldehyde in injectable pharmaceutical formulations by solid-phase microextraction coupled with gas chromatography–flame ionization detector. Polyaniline was electrodeposited on a platinum wire in trifluoroacetic acid solvent by cyclic voltammetry technique. This fiber shows high thermal and mechanical stability and high performance in extraction of benzaldehyde. Extraction and desorption time and temperature, salt effect and gas chromatography parameters were optimized as key parameters. At the optimum conditions, the fiber shows good linearity between peak area ratio of benzaldehyde/3-chlorobenzaldehyde and benzaldehyde concentration in the range of 50–800 ng/mL with percent relative standard deviation values ranging from 0.75 to 8.64% (n 5 3). The limits of quantitation and detection were 50 and 16 ng/mL, respectively. The method has the requisite selectivity, sensitivity, accuracy and precision to assay benzaldehyde in injectable pharmaceutical dosage forms.
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  • Date Issued: 2014

Electrospun fiber based colorimetric probes for aspartate aminotransferase and I7ß-estradiol

  • Authors: Pule, Bellah Oreeditse
  • Date: 2014
  • Language: English
  • Type: text , Thesis , Doctoral , PhD
  • Identifier: http://hdl.handle.net/10962/54869 , vital:26623
  • Description: Fabrication, characterization and application of electrospun polymer composite based colorimetric probes are presented in this thesis. The first part of the thesis involved the development of a protocol for in situ reduction of gold trication (Au³+) into metallic gold atoms with sodium borohydride. The prepared PS-Au NPs showed an SPR band at 542 nm. Furthermore the absorbance of the colloidal Au NPs in polystyrene exhibited a good linear correlation (r2 = 0.9934) to E2 concentration in the range 5 to 50 ppb. The lowest naked eye detection limit was found to be 0.5 ppb and could further be easily monitored by UV-vis spectrophotometer. Upon interaction with E2 Au NPs aggregated to give nanoparticle clusters, confirmed through TEM analysis. Different concentrations of Au NPs were found to have a significant effect on the conductivity of the PS-Au NPs solution. At low concentrations of Au NPs (0.002, 0.015 and 0.025% w/v) PS-Au NPs solution could be electrospun without clogging. The FE-SEM images showed a non-beaded morphology of PS-Au NPs composite fibers. Upon interaction of the colorimetric probe strips with various E2 concentrations it was observed that with increasing E2 concentrations (50 ng/ml to 1000 µg/ml) the colour of the probe changed gradually from white to shades of pink and eventually to shades of blue at higher E2 concentrations. The visible cut-off concentration was 100 ng/ml. The second component of the thesis focussed on the development of diazonium dye-nylon 6 colorimetric probe for aspartate aminotransferase. At optimal pH 7.4 the enzyme was stable, highly active and catalyzed a reaction that was susceptible to detailed kinetic analysis by continuous optical methods. The KM values for L-aspartate, a- ketoglutarate and oxaloacetate were 2.60, 0.59 and 0.066 mM, respectively. On the basis of these KM values the solid-state colorimetric probe was developed. A colour change occurred when an electrospun dye-N 6 probes were exposed to visibly detectable concentrations of oxaloacetate, an AST-catalyzed reaction product. While monitoring AST activity at 530 run, a linear relation was obtained between oxaloacetate concentrations ranging from 0.4 - 7.4 µg/ml. Naked eye detection limit of 2.4 µg/ml oxalaoacetate equivalence of 10 times the normal AST activity was attained. The colorimetric probe was in addition, tested against co-substrates aspartate, ketoglutarate and a variety of other compounds such as alanine, pryruvate, as well as glutamic, malaic and succinic acids known to interfere with AST activity. Each compound elicited a distinct and unambiguous colour change upon interaction with the colorimetric probe. Further X-ray powder diffraction (XRD), duNouy ring tensiometer, Brunauer- Emmett- Teller (BET) and energy dispersive X-ray spectroscopy (EDS/EDX) characterization confirmed composition and stability of the colorimetric probes. Colorimetric probes developed in this thesis are relatively cost effective, simple and "rugged" for measurement of analytes with visual detection without sample pretreatment in matrices, such as plasma and dairy effluents. The probes warrant further investigation as they have shown potential and offer a promising solid-state platform for both clinical diagnostics and environmental monitoring.
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  • Date Issued: 2014

Electrospun fibre based colorimetric probes for biological molecules

  • Authors: Mudabuka, Boitumelo
  • Date: 2014
  • Subjects: Nanofibers , Vitamin C , Dopamine
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4535 , http://hdl.handle.net/10962/d1016354
  • Description: The thesis reports the use of electrospun nanofibres as a platform for the development of colorimetric probes. Three colorimetric probes in the form of electrospun nanofibre test strips were developed for the selective detection of ascorbic acid and dopamine because they are crucial biomolecules for physiological processes in human metabolism and usually coexist in biological samples. The simultaneous detection of the biomolecules is very important as their abnormal concentration levels would lead to diseases such as Parkinson's and schizophrenia. Different methods of incorporating detector agents into the nanofibre were exploited for the detection of the biomolecules. The methods included physical incorporation of nanoparticles, covalent bonding of ligand/dyes through surface modification of the fibres. The first colorimetric test strip for ascorbic acid was based on copper-gold alloy nanoparticles prepared in-situ and hosted in nylon6. The test strip showed selectivity in detecting ascorbic acid in the pH range 2 – 7. The suitability of fibres in hosting copper-gold alloy nanoparticles for the colorimetric detection of ascorbic acid was investigated using nylon6, poly(vinyl benzyl chloride)-styrene and cellulose acetate based test strips. All the test strips exhibited leaching and the nylon6 based test strip was found to be thermally stable up to 60 ˚C. The colorimetric performance of the test strips was maintained and neither was colour decay exhibited after 10 months of storage in a shelf. The test strip achieved an eye-ball limit of detection of 1.76 x10-2 mg L-1 and its suitability was demonstrated by the determination of ascorbic acid in fruit juices, urine, serum, and vitamin C tablets. The second colorimetric test strip for ascorbic acid and dopamine employed prussian blue synthesised in-situ in nylon6. Ascorbic acid turned the deep blue test strip to light blue at pH 3, and a faded navy blue colour at a pH range of 6 - 7 while dopamine changed the strip to purple at the same pH range. The versatility of the test strip was demonstrated by detecting ascorbic acid in commercial fruit juices as well as by detecting ascorbic acid as well as dopamine in fortified urine. The eye-ball detection limit of the Prussian blue test strip for ascorbic acid and dopamine was 17.6 mg L-1 and 18.9 mg L-1, respectively. The third method involved a covalent approach, where poly(vinylbenzyl chloride) nanofibers were post functionalised with 2-(2′-pyridyl)-imidazole and iron(III) for the selective detection of ascorbic acid and dopamine. The eye-ball detection limit for ascorbic acid and dopamine was 17.6 mg L-1 and 18.9 mg L-1, respectively. The test strip was selective for dopamine, but the detection of ascorbic acid suffered from interference by glutathione. The application of the test strips was nevertheless demonstrated by the detection of ascorbic acid in fruit juices and dopamine in fortified urine. The developed test strips employing the three approaches were applied without sample pre-treatment and use of supporting equipment.
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  • Date Issued: 2014

Electrospun nanofibers as solid phase extraction sorbents and support for alkylphenols colorimetric probes

  • Authors: Tancu, Yolanda
  • Date: 2014
  • Subjects: Nanofibers , Electrospinning , Extraction (Chemistry) , Sorbents , Phenols , Colorimetry , Transmission electron microscopy , High resolution spectroscopy
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4486 , http://hdl.handle.net/10962/d1012997
  • Description: The thesis reports on fabricating alternative solid phase extraction (SPE) sorbents and colorimetric probes based on electrospun nanofibers for alkylphenols (APs). Hydroxyl methylated styrene [poly(co-styrene-CH₃OH)] and 3-oxobutanoate styrene [poly(co-styrene-OCOCH₃COCH₃)] copolymers were synthesized and fabricated into sorbent materials by electro-spinning/spraying. The fabricated morphologies consisting of bead free fibers, beaded fibers and particles were evaluated as SPE sorbents using batch experiments. Electropun fibers proved to be better sorbents as they exhibited extraction efficiency that exceeded 95% compared to 60% for beaded fibers and 40% for particles. In view to reduce sample and solvent volumes, smooth fibers were packed into pipette tips as SPE devices that yielded quantitative recoveries of APs from spiked wastewater samples. Recoveries ranged from 70% to 125% with LOD of 0.008, 0.01 and 0.1 μg mL⁻¹ for 4-tert octylphenol (4-t-OP), 4-octylphenol (4-OP) and 4-nonylphenol (4-NP) respectively, when using high performance liquid chromatography-fluorescence detector (HPLC-FLD). Furthermore, amino functionalised polydiacetylene polymers (PDAs), citrate capped gold (AuNPs) and silver nanoparticles (AgNPs) were evaluated as colorimetric probes for visual detection of APs. In colloidal studies, AuNPs probe showed a colour change from wine red to green upon introduction of analyte. UV-vis spectroscopy revealed the shifting of the surface plasmon resonance (SPR) peak from 525 nm to 729 nm induced by aggregation of AuNPs. For AgNPs probe, a colour change was observed from yellowish green to brown. Transmission electron microscopy (TEM) studies showed growth of AgNPs. A presumed oxidation of the analyte, forming an absorbing compound at 279 nm in both AgNPs and PDAs probes was also observed. For PDAs probe the colour change was from purple to pink. Concentrations as low as 30 μg mL⁻¹ were detectable in all colloidal based probes. Further colorimetric investigations were conducted with electrospun AuNPs-nylon 6 fiber mat. A colour change from purplish red to navy blue at concentrations of 1000 μg mL⁻¹ was observed. Electrospun AgNPs –nylon 6 fiber mat did not show a distinct colour change. High resolution scanning electron microscopy (HRSEM) revealed the analyte inducing the assembly of AuNPs and AgNPs as they covered the surface of the nanofiber mat. Electrospun nanofibers are a platform for analysis and thus tuning their chemistry will lead to sensitive and selective methods
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  • Date Issued: 2014

Electrospun sorbents for solid phase extraction (SPE) and colorimetric detection of pesticides

  • Authors: Gulamussen, Noor Jehan
  • Date: 2014
  • Subjects: Sorbents , Electrospinning , Extraction (Chemistry) , Colorimetry , Pesticides , Water -- Pesticide content -- Research
  • Language: English
  • Type: Thesis , Masters , MSc
  • Identifier: vital:4501 , http://hdl.handle.net/10962/d1013241
  • Description: The thesis presents the evaluation of polysulfone sorbents for solid phase extraction (SPE) and the development of colorimetric probes for pesticides analysis in water. Through electrospraying and electrospinning techniques, different morphologies of sorbents (particles, beaded fibers and bead-free fibers) were fabricated. The sorbents were morphologically characterized by scanning electron microscopy. Adsorption capacities of sorbents were evaluated by conducting recoveries studies for model pesticides; atrazine, chlorpyrifos and DDT using batch and column SPE modes. Better recovery results were achieved by employing the batch mode of fibers, as values ranged from 98 to 105percent. Further sorbent evaluation was conducted using breakthrough experiments and static experiments. The breakthrough studies indicated that 1700 μL was the sample volume that could be percolated with no breakthrough of the analyte that correspond to a concentration of 150 mg/g of sorbent that can be extracted without any loss of analyte. From static studies, quantities of each model compound adsorbed into the fiber at the equilibrium time were evaluated. The adsorbed atrazine was 65, chlorpyrifos 250 and DDT 400 mg/g of sorbent. Kinetic studies suggested retention mechanism following pseudo first and second order model observed by high correlation coefficients (> 0. 96), demonstrating the fiber affinity to retain both polar and non-polar compounds opening a possibility to be used as sorbent for sample preparation of different classes of pesticides in water. For the second part of the study simple strategies for colorimetric sensing based on silver nanoparticles and polivinylpyrrolidone capped nanoparticles were developed, respectively for atrazine and chlorpyrifos detection. The limits of detection of the methods were 3.32 and 0.88 mg/L for atrazine and chlorpyrifos respectively. The applicability of the probe in real samples was demonstrated by the recoveries studies of tap water varying from 94 to 104 percent. The versatility of the probe was demonstrated by affording a simple, rapid and selective detection of atrazine and chlorpyrifos in the presence of other pesticides by direct analysis without employing any sample handling steps. Attempt to incorporate the probes in a solid support was achieved by using nylon 6 as solid support polymer proving to be fast and useful for on-site detection.
  • Full Text:
  • Date Issued: 2014

Electro‐oxidation of acetaminophen on nickel/poly (o‐aminophenol)/multi‐walled carbon nanotube nanocomposite modified graphite electrode.

  • Authors: Naeemy, Ali , Mohammadi, Ali , Bakhtiari, Hediech , Ashouri, Nasim , Walker, Roderick B
  • Date: 2014
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/184107 , vital:44173 , xlink:href="https://ietresearch.onlinelibrary.wiley.com/doi/pdf/10.1049/mnl.2014.0197"
  • Description: Poly(o-aminophenol) (POAP)/multi-walled carbon nanotube (MWCNT) nanocomposite and POAP in the absence of the MWCNT were fabricated by consecutive cyclic voltammetry (CV) on a graphite (G) electrode. The dispersion of nickel (II) ions was accomplished and incorporated into the polymeric electrodes (G/POAP and G/POAP-MWCNT) by immersing them into a 0.1 M nickel (II) solution. Following preparation of G/POAP/Ni and G/POAP-MWCNT/Ni, the electrochemical behaviour was examined using CV. Scanning electron microscopy was used for characterisation of the nanocomposite. The prepared electrodes showed enhanced electrocatalytic activity for the oxidation of acetaminophen and facilitated the detection of acetaminophen in a 0.1 M NaOH solution. Compared with the G/POAP/Ni electrode, the G/POAP-MWCNT/Ni electrode had a significant current response of acetaminophen oxidation because of the synergistic effects of POAP and the MWCNT. By CV, the calibration plot was linear in the range of 1–13 mM with standard deviation between 0.3 and 6.54% for acetaminophen. The G/POAP-MWCNT/Ni was successfully applied for acetaminophen determination in tablets and the results showed sufficient precision and achieved a mean recovery of 96.8% (R.S.D. = 4.9%).
  • Full Text:
  • Date Issued: 2014

Elephants in Africa: Big, grey biodiversity thieves?

  • Authors: Kuiper, Timothy R , Parker, Daniel M
  • Date: 2014
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/124385 , vital:35601 , https://doi.org/10.2989/16085914.2011.589120
  • Description: The conservation of biological diversity is one of the greatest challenges facing humanity today.1,2 Addressing this challenge must inevitably involve the maintenance of the composition, structure and functioning of multi-species ecosystems.2-4 While preventing the loss of particular species is an obvious strategy, a second goal might be to manage for local species diversity and the heterogeneity of habitats.5 A further objective may be the restoration of damaged ecosystems.6 Large herbivore assemblages form an important component of many diverse ecosystems and are of distinct ecological, and hence conservation, value.7-9 On the other hand, herbivores managed at unnaturally high densities may drive detrimental changes in the structural heterogeneity of habitats.10-12 Thus, decision-makers are faced with the challenge of balancing the needs of populations of large herbivores with the preservation of vegetation and ecosystem diversity.9 In light of these considerations, conclusions as to whether large herbivores are ‘good’ or ‘bad’ for biological diversity are both contentious and elusive. Nonetheless, we seek to explore this question with particular reference to African savannah elephants (Loxodonta africana). We discuss whether or not the elephant should be considered a biodiversity thief – a species that upsets the natural diversity of life in the habitat in which it lives.
  • Full Text:
  • Date Issued: 2014

Elephants in Africa: Big, grey biodiversity thieves?

  • Authors: Kuiper, T R , Parker, Daniel M
  • Date: 2014
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/69886 , vital:29591 , http://dx.doi.org/10.1590/ sajs.2014/a0058
  • Description: The conservation of biological diversity is one of the greatest challenges facing humanity today.1,2 Addressing this challenge must inevitably involve the maintenance of the composition, structure and functioning of multi-species ecosystems.2-4 While preventing the loss of particular species is an obvious strategy, a second goal might be to manage for local species diversity and the heterogeneity of habitats.5 A further objective may be the restoration of damaged ecosystems.6 Large herbivore assemblages form an important component of many diverse ecosystems and are of distinct ecological, and hence conservation, value.7-9 On the other hand, herbivores managed at unnaturally high densities may drive detrimental changes in the structural heterogeneity of habitats.10-12 Thus, decision-makers are faced with the challenge of balancing the needs of populations of large herbivores with the preservation of vegetation and ecosystem diversity.9 In light of these considerations, conclusions as to whether large herbivores are 'good' or 'bad' for biological diversity are both contentious and elusive. Nonetheless, we seek to explore this question with particular reference to African savannah elephants (Loxodonta africana). We discuss whether or not the elephant should be considered a biodiversity thief - a species that upsets the natural diversity of life in the habitat in which it lives. The African elephant has been driven to local extinction over much of its former range, with hunting for meat and ivory and the conversion of elephant habitat to agriculture constituting the major drivers.5 Given the historical decline in elephant numbers, the conservation of this species appears to be a sensible objective.9,13 However, the protection afforded to elephants in confined (usually fenced) reserves across Africa has distinct implications for the management of local species diversity and the heterogeneity of habitats.14,15 Elephants have been shown to have clear impacts on the structure of vegetation, particularly in woodland habitats12,16,17, and these changes may have knock-on effects for sympatric species10,18,19. The effects of elephants on biological diversity in protected areas are of particular concern in light of how expansion in human populations, and the land-use change that follows, places increasing pressure on reserves to preserve biological diversity.9,10. Change within ecosystems is natural and inevitable and large herbivores have been living in an ever-changing environment for millions of years.20 Changes brought on by elephants, therefore, should not automatically be categorised as undesirable, and short-term changes may be part of an overarching trend of long-term stability.8,21 Furthermore, current elephant impacts can only be adequately assessed in the light of historical (on the scale of centuries) benchmarks, for which accurate information is notoriously scant.10,21 The current impacts of elephant populations on vegetation dynamics in some regions may in fact represent a shift towards a more natural historical state.8,21 Finally, much of the detrimental impacts of elephants on habitat structure and diversity, particularly at smaller scales, has resulted from human interventions (such as the erection of fences and the establishment of artificial water points) that have unnaturally confined elephants to localised areas, disrupted seasonal movements and disturbed the natural dynamics of population processes.5,13,22.
  • Full Text:
  • Date Issued: 2014

Embracing racial reasoning: the DASO poster controversy and ‘Race’politics in contemporary South Africa

  • Authors: Vincent, Louise , Howell, Simon
  • Date: 2014
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/141933 , vital:38017 , DOI: 10.1080/03057070.2014.877651
  • Description: We examine the response to a poster published by South Africa's official opposition's youth wing, the Democratic Alliance's Student Organisation (DASO) as part of a political campaign in 2012. From commentary that the poster's publication generated, we excavate some of the key discursive strategies used by commentators to negotiate the gulf between the constitutional value of non-racialism and the lived contemporary reality of race in South Africa. Many commentators situated themselves either as ‘colour-blind’, or reformulated ‘race’ as ‘class’ or ‘culture’. In making visible some of these strategies, and the attendant (re-)racialised narratives upon which they rely, we highlight the paradoxes that inhere in the idea of ‘non-racialism’ – a notion that implies that race must simultaneously be thought and ‘un-thought’. Racial categories contrived by apartheid have been somewhat rearranged and rearticulated, but nevertheless continue to operate today as organising principles.
  • Full Text:
  • Date Issued: 2014
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