Development and evaluation of a web application employing artificial neural networks to facilitate the prediction of antiretroviral drug resistance in patients infected with HIV-1 subtype B
- Authors: Nabatanzi, Margaret
- Date: 2018
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63396 , vital:28406
- Description: Expected release date-April 2019
- Full Text:
Development and optimisation of a novel Plasmodium falciparum Hsp90-Hop interaction assay
- Authors: Wambua, Lynn
- Date: 2018
- Subjects: Plasmodium falciparum , Molecular chaperones , Heat shock proteins , Protein-protein interactions , Antimalarials
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/62626 , vital:28216
- Description: Protein-protein interactions are involved in a range of disease processes and thus have become the focus of many drug discovery programs. Widespread drug resistance to all currently used antimalarial drugs drives the search for alternative drug targets with novel mechanisms of action that offer new therapeutic options. Molecular chaperones such as heat shock proteins facilitate protein folding, play a role in protein trafficking and prevent protein misfolding in cells under stress. Heat shock protein 90 (Hsp90) is a well-studied chaperone that has been the focus of cancer drug development with moderate success. In Plasmodium falciparum (P. falciparum), heat shock proteins are thought to play a vital role in parasite survival of the physiologically diverse habitats of the parasite lifecycle and because Hsp90 is prominently expressed in P. falciparum, the chaperone is considered a potentially ideal drug target. Hsp90 function in cells is regulated by interactions with co-chaperones, which includes Heat shock protein 70-Heat shock protein 90 organising protein (Hop). As opposed to directly inhibiting Hsp90 activity, targeting Hsp90 interaction with Hop has recently been suggested as an alternative method of Hsp90 inhibition that has not been explored in P. falciparum. The aim of this research project was to demonstrate PfHsp90 and PfHop robustly interact in vitro and to facilitate high-throughput screening of PfHsp90-PfHop inhibitors by developing and optimising a novel plate capture Hsp90-Hop interaction assay. To establish the assay, the respective domains of the proteins that mediate Hsp90-Hop interaction were used (Hsp90 C- terminal domain and Hop TPR2A domain). The human Hsp90 C-terminal domain and glutathione-S-transferase (GST) coding sequences were cloned into pET-28a(+) and murine and P. falciparum TPR2A sequences into pGEX-4T-1 plasmids to enable expression of histidine-tagged and GST fusion proteins, respectively, in Escherichia coli. The P. falciparum Hsp90 C-terminal domain sequence cloned into pET-28a(+) was supplied by GenScript. The constructs were transformed into T7 Express lysYcompetent E. coli cells and subsequent small- scale expression studies showed the recombinant proteins were expressed in a soluble form allowing for subsequent protein purification. Purification of the recombinant proteins was achieved using nickel-NTA and glutathione affinity chromatography for the His-tagged (Hsp90 C-terminal domains and GST) and GST fusion proteins (TPR2A domains), respectively. The purified proteins were used to establish and optimise mammalian and P. falciparum Hsp90- Hop interaction assays on nickel-coated plates by immobilising the His-tagged C-terminal domains on the plates and detecting the binding of the GST-TPR2A domains using a colorimetric GST enzyme assay. Z’-factor values above 0.5 were observed for both assays indicating good separation between the protein interaction signals and negative control background signals, although relatively high background signals were observed for the mammalian interaction due to non-specific binding of murine TPR2A to the plate. Designed human and P. falciparum TPR peptides were observed to be effective inhibitors of the mammalian and P. falciparum interactions, demonstrating the assay’s ability to respond to inhibitor compounds. Comparison of assay performance using GST assay kit reagents and lab- prepared reagents showed the assay was more efficient using lab-prepared reagents, however, lower GST signals were observed when comparing assay performance using a custom prepared Ni-NTA plate to a purchased Ni-NTA plate. The Hsp90-Hop interaction assays were also performed using an alternative assay format in which the GST-TPR2A fusion proteins were immobilised on glutathione-coated plates and binding of the His-tagged C-terminal domains detected with a nickel-horseradish peroxidase (HRP) conjugate and a colorimetric HRP substrate. The assay showed higher interaction signals for the P. falciparum proteins but comparatively low signals for the mammalian proteins. Z’-factor values for the assay were above 0.8 for both protein sets, suggesting this assay format is superior to the GST assay. However, further optimisation of this assay format is required. This study demonstrated direct binding of PfHsp90-PfHop in vitro and established a novel and robust PfHsp90-PfHop interaction assay format that can be used in future screening campaigns.
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Development and validation of a health literacy measure for limited literacy public sector patients in South Africa
- Authors: Marimwe, Chipiwa
- Date: 2018
- Subjects: Health literacy -- South Africa , Patient education -- South Africa , Communication in medicine -- South Africa , Health literacy -- Social aspects -- South Africa , Poor -- Medical care -- South Africa , Analysis of variance , Multidimensional Screener of Functional Health Literacy (MSFHL)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/62661 , vital:28227
- Description: The growing complexity of healthcare demands greater patient involvement and skills to navigate this complex system. It has therefore become increasingly important to identify individuals with inadequate health literacy, by using efficient, short and reliable measures for doing so. Most research on the development and validation of health literacy tests has been conducted in high-income countries, with very little reported from low-and middle-income countries (LMICs). Existing health literacy measures have come under scrutiny for their lack of cultural sensitivity, bias towards certain population groups and failure to acknowledge health literacy as a multidimensional concept. These measures usually have limited application in LMICs due to the significantly different structuring of healthcare systems, they overlook the extreme discrepancies in educational levels, and rely too heavily on the ability to read health information. No health literacy data for South Africa are available, and only a few health literacy-based research papers have been published in this country. The aim of the study was to develop and validate a health literacy measure that is contextually and culturally appropriate to measure health literacy in limited literacy public sector patients in South Africa. An Item Bank of 30 questions was developed with the input of a diverse expert consultant panel, and included skills-based and self-reported questions which ensured cultural, contextual and educational level appropriateness. The Information and Support for Health Actions Questionnaire (ISHA-Q) is a health literacy measure developed to assess health literacy for LMICs which includes 14 core scales. These were useful in ensuring coverage of a range of health literacy constructs within the Item Bank. The 30 questions were then allocated to one of three health literacy domains: Procedural knowledge, Factual knowledge and Access to healthcare, health services and social support. Ethical approval for the study was obtained. The questions were translated into isiXhosa and underwent pilot testing. Following pilot testing, 120 isiXhosa first-language speakers, at least 18 years old, who attended public sector facilities and had a maximum 12 years of education were recruited from a primary healthcare clinic in Grahamstown. An interpreter was trained and he participated in all interviews. A questionnaire was used to collect data on the 30-question Item Bank. The Multidimensional Screener of Functional Health Literacy (MSFHL) was used as the primary comparator.The second phase of the study involved the refinement of the 30 questions in the Item Bank, which involved a multi-stage process. Data were analysed statistically using t-test, correlations, chi-square and ANOVA tests at a 5% level of significance, in order to identify problematic questions. Item Response Theory was used to ascertain difficulty and discriminatory ability of the questions. Each question was further subjected to in-depth interrogation by a panel of healthcare professionals to ensure that questions were supported by the conceptual framework and the definitions of health literacy adopted for this study. The number of questions was reduced from 30 to 12, and formed the new Health Literacy Test - Limited Literacy (HELT-LL). To validate the HELT-LL, 210 patients with the same inclusion criteria as previously noted, were recruited from four primary healthcare clinics in the Eastern Cape Province. Individual interviews were conducted with the assistance of the interpreter to collect sociodemographic data as well as data from the HELT-LL, the primary comparator (MSFHL), and a secondary comparator which was a South African modified version of the Newest Vital Sign (NVS-SA). The HELT-LL was re-administered to 40 patients in a follow-up interview two weeks later. The HELT-LL categorised only 17.6% of the patients as having adequate health literacy, just over a third with inadequate health literacy, and the majority with marginal health literacy. Questions in the cognitively demanding Procedural knowledge domain were the most poorly answered, with a mean score of 48.6±24.9%. Patients had great difficulty performing the basic numeric tasks in this domain. The overall mean score for the HELT-LL was 52.8±18.4%, compared with the more cognitively demanding NVS-SA with a mean of 28.6±21.1%, and clearly illustrated the impact of the strategy to include in the HELT-LL a variety of questions with differing cognitive load. The MSFHL, which is based on demographic characteristics and perceived difficulties with reading and writing, had an overall mean score of 44.4±26.2%. Demographic characteristics including age, education and English literacy, were found to be good predictors of limited health literacy, with significant correlations being found between these variables and the mean HELT-LL score. An acceptable value for Cronbach’s alpha, excellent test-retest reliability and excellent concurrent validity show that the HELT-LL is a valid and reliable measure of health literacy in our target population. As there is a paucity of health literacy research emanating from developing countries, this study presents a significant contribution to literature. It is the first study to report the development and validation of a health literacy measure to address the dearth of available health literacy measures applicable for South Africa. If implemented for use in clinical settings and for research purposes, it could provide valuable South African health literacy data which could inform the development of interventions focusing on improving health literacy and health outcomes.
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Development of a computational chemistry scheme for testing the utility of synthetic bacteriochlorin in dye-sensitized solar cells
- Authors: Kota, Ntsika
- Date: 2018
- Subjects: Dye-sensitized solar cells , Computational chemistry , Density functionals , Electronic excitation , Molecular orbitals , Oscillator strengths , Bacteriochlorin
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/62327 , vital:28155
- Description: A computational chemistry scheme, based on density functional theory, was developed for in silico testing of a few bacteriochlorin properties relevant to dye-sensitized solar cells. These properties included electronic excitation wavelengths, molecular orbital energy levels, and oscillator strengths among others. Comparisons were made among four species, using computational proxies for electron injection quantum yield and photo-induced current production. The proxy measures for current production (frontier orbital energy level and short circuit current) made consistent, though qualitative, predictions about the ranking of the four dyes. The proxy measures for electron injection quantum yield (change in planar dipole moment and density of states) made less categorical predictions about the ranking. Overall, the scheme singled out one dye as the worst, but made no conclusive predictions about the relative ranking of the other three. There was insufficient data for comparison of the ranking predictions with experiment.
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Development of a low-cost bioprinting system for the fabrication of cell-laden sodium alginate hydrogels
- Authors: Honiball, John Robert
- Date: 2018
- Subjects: Regenerative medicine , Tissue engineering , Alginates , Colloids , Three-dimensional printing
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/59204 , vital:27470
- Description: Bioprinting is a rapidly expanding technology with the ability to fabricate in vitro 3D tissues in a layer-by-layer manner to ultimately produce a living tissue which physiologically resembles native in vivo tissue functionality. Unfortunately, large costs associated with commercially available bioprinters severely limit the amount of people/research groups with access to the technology. Here, we investigated the potential for modifying a commercially available RepRap Prusa iteration 3 (i3) three-dimensional (3D) printer, by replacing the traditional plastic-based print-head with various open-source syringe-housed microextrusion print-head units, such that deposition of composite bioinks consisting of cells, biopolymer scaffolds and/or biomolecules may be achieved at a relatively low cost. Using adipose-derived human mesenchymal stromal stem cells (ad-HMSC) induced for adipogenic differentiation, as well as human umbilical vein endothelial cells (HUVEC), the potential for fabricating vascularised adipose tissue was investigated. The non-toxic, inexpensive algal polysaccharide, sodium alginate, was used to test the printability of the system, as well as for investigating the functionality unmodified sodium alginate has for use as a potential bioink in adipose tissue engineering. Cell viability assays, namely WST-1 and fluorescein diacetate (FDA)/propidium iodide (PI) live/dead cell staining, revealed that ad-HMSC were viable after 7 days of culture. However, viability of HUVEC encapsulated hydrogels revealed significantly lower cell viability. Live/dead cell staining revealed that the modified printing system was able to print ad-HMSC/HUVEC co-cocultures with a large degree of cell viability after 1 day of culture. However, after 7 days of culture, the majority of cells were revealed to be dead. Furthermore, due to the lack of mechanical integrity possessed by alginate in a liquid-like state, printing sodium alginate hydrogels in air consistently resulted in deformation of printed constructs. The newly developed 3D printing technique termed freeform reversible embedding of suspended hydrogels (FRESH) was therefore investigated as a means for achieving 3D spatial control of printed hydrogels using the modified system. Printing cell-free sodium alginate hydrogels within gelatin sacrificial support baths allowed for fabricating constructs in a spatially defined manner. However, overprinting and swelling of alginate hydrogels negatively affected the overall printing accuracy. The present study aimed to pave the way for further system modifications and refinements, such that the ultimate goal of low-cost bioprinting may be achieved. Further optimisation of printing parameters, hydrogel characteristics and sterilisation techniques may allow for fabricating viable, physiologically relevant tissues using the modified system developed.
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Development of a Postharvest Cold Treatment for Cryptophlebia peltastica (Lepidoptera: Tortricidae) for Export of Litchis From South Africa
- Authors: Moore, Sean D , Kirkman, Wayne , Peyper, Mellissa , Thackeray, Sean R , Marsberg, Tamryn , Albertyn, Sonnica , Hill, Martin P
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/423729 , vital:72089 , xlink:href="https://doi.org/10.1093/jee/toy287"
- Description: The litchi moth, Cryptophlebia peltastica (Meyrick) (Lepidoptera: Tortricidae), is endemic to sub-Saharan Africa and certain Indian Ocean islands. It is an important pest of litchis and to a lesser extent macadamias. Litchis are exported to certain markets that consider C. peltastica as a phytosanitary pest. Consequently, an effective postharvest phytosanitary treatment is required. This study sought to develop a cold disinfestation treatment for this purpose. First, it was established that the fifth instar was the most cold-tolerant larval stage, as it was the only instar for which there was still some survival after 12 d at 1°C. It was then determined that cold treatment trials could be conducted in artificial diet, as there was no survival of fifth instar C. peltastica in litchis after only 9 d at 1°C, whereas it took 15 d at this temperature before no survival of fifth instar C. peltastica was recorded in artificial diet. Consequently, cold susceptibility of fifth instar C. peltastica and the most cold-tolerant larval stages (fourth and fifth instar) of false codling moth, Thaumatotibia leucotreta (Meyrick) (Lepidoptera: Tortricidae), were compared in artificial diet. There was no survival of C. peltastica after 13 d at 1°C, whereas this was only so for T. leucotreta after 16 d. Consequently, it can be concluded that any cold treatment that has been proven effective against T. leucotreta would be as effective against C. peltastica. Finally, it was confirmed that the cold susceptibility of T. leucotreta in artificial diet did not overestimate the effect of cold on T. leucotreta larvae in litchis.
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Development of an LCT-Based MOOC Taxonomy
- Authors: Motara, Yusuf, M
- Date: 2018
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/428972 , vital:72550 , https://doi.org/10.1145/3289406.3289411
- Description: Codecademy is an example of a successful and disruptive player in the online education space. This work describes the structure, content, and experience of working through a Codecademy Pro Intensive module and compares it to the offline approach in a similar domain. Existing taxonomies are insufficiently general to explain its success, and a new taxonomy based on Legitimation Code Theory is developed to compensate. This taxonomy is arguably more meaningful and more general than those presently in use.
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Developmental and reproductive performance of a specialist herbivore depend on seasonality of, and light conditions experienced by, the host plant
- Authors: Zachariades, Uyi O O, , Heshula, Lelethu U P , Hill, Martin P
- Date: 2018
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59845 , vital:27667 , https://doi.org/10.1371/journal.pone.0190700
- Description: Host plant phenology (as influenced by seasonality) and light-mediated changes in the phenotypic and phytochemical properties of leaves have been hypothesised to equivocally influence insect herbivore performance. Here, we examined the effects of seasonality, through host plant phenology (late growth-season = autumn vs flowering-season = winter) and light environment (shade vs full-sun habitat) on the leaf characteristics of the invasive alien plant, Chromolaena odorata. In addition, the performance of a specialist folivore, Pareuchaetes insulata, feeding on leaves obtained from both shaded and full-sun habitats during autumn and winter, was evaluated over two generations. Foliar nitrogen and magnesium contents were generally higher in shaded plants with much higher levels during winter. Leaf water content was higher in shaded and in autumn plants. Total non-structural carbohydrate (TNC) and phosphorus contents did not differ as a function of season, but were higher in shaded foliage compared to full-sun leaves. Leaf toughness was noticeably higher on plants growing in full-sun during winter. With the exception of shaded leaves in autumn that supported the best performance [fastest development, heaviest pupal mass, and highest growth rate and Host Suitability Index (HSI) score], full-sun foliage in autumn surprisingly also supported an improved performance of the moth compared to shaded or full-sun leaves in winter. Our findings suggest that shaded and autumn foliage are nutritionally more suitable for the growth and reproduction of P. insulata. However, the heavier pupal mass, increased number of eggs and higher HSI score in individuals that fed on full-sun foliage in autumn compared to their counterparts that fed on shaded or full-sun foliage in winter suggest that full-sun foliage during autumn is also a suitable food source for larvae of the moth. In sum, our study demonstrates that seasonal and light-modulated changes in leaf characteristics can affect insect folivore performance in ways that are not linear.
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Digital Inclusion: A model for e-Infrastructure and e-Services in Developing Countries
- Authors: Terzoli, Alfredo , Siebörger, Ingrid , Tsietsi, Mosiuoa , Gumbo, Sibukelo
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/430973 , vital:72733 , https://doi.org/10.1007/978-3-319-98827-6_7
- Description: A large portion of the South African population is still not connected in a productive manner to the Internet, despite the existence of a govern-ment plan for public broadband, ‘SA Connect’. One reason for this could be the lack of an appropriate model, through which connectivity can be diffused in a meaningful way through all areas of South Africa. This paper presents the model developed over more than a decade of experimentation in real life settings in the Siyakhula Living Lab, a joint venture between the universities of Rhodes and Fort Hare, South Afri-ca. The model proposes the ‘Broadband Island’ as basic e-infrastructure unit, which clusters nearby points-of-presence hosted in schools. In each Broadband Island is located an applications integra-tion platform, TeleWeaver, which monetizes channels of access to the local community, to support the e-infrastructure while providing useful services to the population and the Government.
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Discontinuous gully erosion as a mechanism of wetland formation: a case study of the Kompanjiesdrif basin, Kromrivier, Eastern Cape, South Africa
- Authors: Lagesse, Juliette V
- Date: 2018
- Subjects: Arroyos -- South Africa -- Kromme River (Eastern Cape) , Arroyos -- Erosion -- South Africa -- Kromme River (Eastern Cape) , Climatic geomorphology -- South Africa -- Kromme River (Eastern Cape) , Sedimentation and deposition -- South Africa -- Kromme River (Eastern Cape) , Alluvial fans -- South Africa -- Kromme River (Eastern Cape) , Wetland ecology -- South Africa -- Kromme River (Eastern Cape) , Rhizophoraceae , Palmiet (Prionium serratum)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/60540 , vital:27791
- Description: The Kompanjiesdrif basin is an unchannelled valley bottom palmiet wetland located near the headwaters of the Kromrivier in the Eastern Cape of South Africa. The wetland itself is underlain by Bokkeveld shales with the bordering mountain ranges comprising more resistant Table Mountain Group quarzitic sandstones. The valley is relatively planar and broad in form over a width of approximately 200 m. None of the existing controls that are considered to lead to valley widening and longitudinal slope reduction are immediately apparent. The basin lies on the Post Africa II erosion surface; with no evidence of a resistant lithology which might act as a local base level, limiting rates of vertical erosion and inducing lateral planing in upstream reaches via a meandering channel. The possible role of sagging of the basin due to long term deep chemical weathering of bedrock is discounted as the lithologies in the basin are sedimentary in origin and thus not susceptible to chemical weathering. The degree to which climate and sea level changes affected rates of incision and subsequent slope reduction is unclear, although their potential influence should be acknowledged. This study examined the geomorphic dynamics as discerned from the sedimentary record and morphology of the wetland basin, which provide a snapshot into the long-term processes which lowered the longitudinal slope and widened this valley. Coring within the wetland to depths of 1 - 3.3 m revealed that the sedimentary fill generally comprised an upward fining sequence, with sand or fine sand at the base, grading into silt and clay and organic material in the upper sections of cores. Occasional instances of multiple fine sand layers were observed in a few of the cores. An increase in the organic content of material from the north to the south side of the wetland and the occurrence of multiple thin layers of sand in the stratigraphy, highlighted the role of the northern tributary alluvial fans in influencing valley form. Sediment from north bank alluvial fans seem to periodically, partially impound the wetland basin. Surveyed transects across the wetland basin along with subsurface coring to the depth to refusal, illustrated a localised increase in longitudinal slope downstream of the nodes of tributary alluvial fan deposits, which impinge on the trunk stream basin. Coupled with the presence of deep, drowned, trench-like features (up to 8 m deep) beneath floating mats of palmiet, which were predominantly free of sedimentary fill and found opposite tributary alluvial fans; confirmed that the northern tributaries play a major role in the structure and geomorphic dynamics of the basin. The trench-like features appeared to be remnants of deep, narrow, discontinuous gullies. Dating of sediment from the base of these features (460-7040 BP) confirmed that they were formed prior to European settlement in the area. Therefore, it is suggested that the localised increase in longitudinal slope, caused by sediment deposition on the alluvial fans, transgresses a geomorphic threshold slope and that gully erosion is thus initiated. The process of repeated gully erosion leads to planing of bedrock and longitudinal slope reduction. Gully erosion forms an integral component of a cycle of deposition and incision referred to as “cut-and-fill”. During each iteration of the cycle of cutting and filling, gullies form in novel locations leading to gradual valley widening. Over geological time scales, the planing of bedrock and resultant valley widening creates a broad planar valley with a very low longitudinal slope; producing conditions suitable for unchannelled valley bottom wetland formation.
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Discovery and validation of a CD4 binding aptamer through Crossover SELEX towards the preliminary development of a point-of-care aptasensor for rapid CD4+ T-cell counting
- Authors: Fellows, Tamika
- Date: 2018
- Subjects: Uncatalogued
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63527 , vital:28431
- Description: Expected release date-April 2020
- Full Text:
Donor-acceptor effects on the optical limiting properties of BODIPY dyes
- Authors: Hlatshwayo, Zweli Thabiso
- Date: 2018
- Subjects: Dyes and dyeing -- Chemistry , Photosensitizing compounds -- Therapeutic use , Cancer -- Photochemotherapy , Upconversion nanoparticles (UCNPs)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63368 , vital:28397
- Description: The main objectives of the research described in this thesis were firstly to synthesize and characterize a series of structurally related BODIPY dyes that are potentially suitable for use in applications, secondly to conjugate a carboxylic acid substituted BODIPY dye to amine-functionalized upconversion nanoparticles (UCNPs) through an amide bond to enable singlet oxygen production upon irradiation at 978 nm in the biological window for tissue penetration for biomedical applications, and thirdly to compare the nonlinear optical (NLO) properties of various BODIPY dyes to determine whether push-pull effects enhance their utility for optical limiting (OL) applications. Halogenated BODIPY cores with high singlet oxygen quantum yields were prepared, which absorb in the green portion of the visible region and making it difficult to treat deeper skin tumors in the context of photodynamic therapy (PDT) applications. UCNPs generally absorb in the near-infrared (NIR) region (978 nm), and this is advantageous because, this is where absorption by water, cells and tissues is minimized. NaYF4: Yb/Er/Gd UCNPs were synthesized, amine functionalized and successfully conjugated to a halogenated carboxylic acid functionalized BODIPY. This allowed for favorable Förster resonance energy transfer (FRET) since one of the emission wavelengths of the NaYF4: Yb/Er/Gd UCNPs overlaps with the main absorption band of the BODIPY at 540 nm. The conjugate was irradiated at 978 nm, but instability of the BODIPY dye was observed, which made singlet oxygen quantum yield determination impossible. An enhanced singlet oxygen quantum yield value was observed upon irradiation of the conjugate at 540 nm, suggesting that further studies of this system are warranted. The OL properties of BODIPY cores and dyes, which are π-extended at the 3,5-positions with styryl groups, were studied in a series of different organic solvents at 532 nm by using the z-scan technique on a nanosecond timescale. Many of the dyes were used to compare the effects of introducing electron donor and acceptor groups on the OL properties of the dyes. The dipole moments of these dyes were found to correlate with the OL response. The OL results indicate that BODIPY dyes with push-pull properties, which are π-extended at the 3,5-positions with styryl groups, can be considered as viable candidates for use in OL applications. The studies sought to establish the effect of ESA in the triplet manifold as compared to the singlet manifold in as far as the OL response is concerned. The most promising dyes were embedded in polystyrene thin films, and this was found to significantly enhance their OL properties.
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Effect of doping vs covalent linking of a low symmetry zinc phthalocyanine to silica nanoparticles on singlet oxygen production
- Authors: Peteni, Siwaphiwe , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187873 , vital:44705 , xlink:href="https://doi.org/10.1016/j.ica.2018.06.029"
- Description: Tris[(4-(pyridin-4-ylthio)-2-thio-4-methylthiazol-5-yl)acetic acid phthalocyaninato] zinc (II) (3) was covalently linked to and doped onto SiNPs. An increase in triplet quantum yields for 3-SiNPs (linked) with decreasing lifetimes was observed. For 3-SiNPs (doped) there was a decrease in both the triplet quantum yield and lifetimes when compared to 3 alone. There was an increase in singlet oxygen quantum yields for 3-SiNPs (linked) compared to 3 from 0.67 to 0.80, while there was a decrease for 3-SiNPs (doped) to 0.25.
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Effect of nature of nanoparticles on the photophysicochemical properties of asymmetrically substituted Zn phthalocyanines
- Authors: Magadla, Aviwe , Oluwole, David O , Britton, Jonathan , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234539 , vital:50206 , xlink:href="https://doi.org/10.1016/j.ica.2018.06.043"
- Description: In this work, low symmetry Zn mono caffeic acid tri-tert butyl (1) and Zn monocarboxyphenoxy tri-(tert-butylphenoxyl) (2) phthalocyanines (Pcs) were covalently linked to amino (using glutathione, GSH, or 3-aminopropyl)triethoxysilane, APTES) functionalised nanoparticles. The nanoparticles are represented as: AgNPs-GSH, SiNPs-APTES, Fe3O4-Ag-SiNPs-APTES and Fe3O4-AgNPs-GSH). The photophysical and photochemical behaviour of the complexes 1 and 2 and their conjugates with nanoparticles were investigated in dimethyl sulfoxide. The conjugates of the Pc complexes with the NPs afforded increase in triplet quantum yields with corresponding decrease in fluorescence quantum yield compared to the Pc complexes alone. The conjugates of 1-AgNPs-GSH, 2-SiNPs-APTES and 2-Fe3O4-Ag-SiNPs-APTES showed higher singlet oxygen quantum yield values as compared to the Pc complexes alone.
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Effect of number of positive charges on the photophysical and photodynamic therapy activities of quarternary benzothiazole substituted zinc phthalocyanine
- Authors: Matshitse, Refilwe , Nwaji, Njemuwa , Mananga, Muthumuni , Prinsloo, Earl , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187819 , vital:44700 , xlink:href="https://doi.org/10.1016/j.jphotochem.2018.08.033"
- Description: The synthesis, photophysicochemical and photodynamic therapy (PDT) activity of quaternary benzothiazole substituted zinc phthalocyanine (2, containing two charges, and 3, containing four charges) are reported in this work. Furthermore, the activity of the synthesized complex was compared to non-quaternary derivative (1). Higher triplet and singlet oxygen quantum yields of 0.92 and 0.85, respectively, for quaternized complexes 2 and 3 compared to complex 1 alone. Complexes 1, 2 and 3 showed relatively no dark toxicity against the epithelial breast cancer cells with cell survival of above 90 ± 3%. The quaternary derivatives (2 and 3) showed superior PDT activity with 30% or less of viable cells at concentration of 50.0 μg/mL in comparison to complex 1 alone which further lay credence to the importance of quaternization in the enhancement of PDT activity.
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Effectiveness of Sampling a Small Sized Network Telescope in Internet Background Radiation Data Collection
- Authors: Chindipha, Stones D , Irwin, Barry V W , Herbert, Alan
- Date: 2018
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/427646 , vital:72453 , https://www.researchgate.net/profile/Barry-Ir-win/publication/327624431_Effectiveness_of_Sampling_a_Small_Sized_Net-work_Telescope_in_Internet_Background_Radiation_Data_Collection/links/5b9a5067299bf14ad4d793a1/Effectiveness-of-Sampling-a-Small-Sized-Network-Telescope-in-Internet-Background-Radiation-Data-Collection.pdf
- Description: What is known today as the modern Internet has long relied on the existence of, and use of, IPv4 addresses. However, due to the rapid growth of the Internet of Things (IoT), and limited address space within IPv4, acquiring large IPv4 subnetworks is becoming increasingly difficult. The exhaustion of the IPv4 address space has made it near impossible for organizations to gain access to large blocks of IP space. This is of great concern particularly in the security space which often relies on acquiring large network blocks for performing a technique called Internet Background Radiation (IBR) monitoring. This technique monitors IPv4 addresses which have no services running on them. In practice, no traffic should ever arrive at such an IPv4 address, and so is marked as an anomaly, and thus recorded and analyzed. This research aims to address the problem brought forth by IPv4 address space exhaustion in relation to IBR monitoring. This study’s intent is to identify the smallest subnet that best represents the attributes found in the/24 IPv4 address. This is done by determining how well a subset of the monitored original subnetwork represents the information gathered by the original subnetwork. Determining the best method of selecting a subset of IPv4 addresses from a subnetwork will enable IBR research to continue in the best way possible in an ever restricting research space.
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Effects of CO2-induced ocean acidification on the early development, growth, survival and skeletogenesis of the estuarine-dependant sciaenid Argyrosomus japonicus
- Authors: Erasmus, Bernard
- Date: 2018
- Subjects: Argyrosomus , Argyrosomus -- Growth , Argyrosomus -- Mortality , Argyrosomus -- Ecology , Argyrosomus -- Physiology , Ocean acidification , Marine ecology -- South Africa , Carbon dioxide -- Physiological effect
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/60585 , vital:27799
- Description: Although it is increasingly accepted that ocean acidification poses a considerable threat to marine organisms, little is known about the likely response of fishes to this phenomenon. While initial research concluded that adult fishes may be tolerant to changes predicted in the next 300 years, the response of early life stages to end-of-century CO2 levels (~ 1100 µatm according to the IPCC RCP 8.5) remains unclear. To date, literature on the early growth and survival of fishes has yielded conflicting results, suggesting that vulnerability may be species dependant. The paucity of ocean acidification research on fishes is particularly evident when one considers larval skeletogenesis, with no robust studies on its impacts on bone and cartilage development. This study addresses the early life embryogenesis, hatching success, growth, skeletogenesis and survival of an estuarine-dependant species. Dusky kob (Argyrosomus japonicus) were reared in a control (pCO2 = 327.50 ± 80.07 qatm at pH 8.15), intermediate (pCO2 477.40 ± 59.46 qatm at pH 8.03) and high pCO2 treatment (pCO2 910.20 ± 136.45 qatm at pH 7.78) from egg to 29 days post-hatch (dph). Sixty individuals from each treatment were sacrificed at the egg stage and at 2, 6, 13, 18, 21 and 26 dph, measured and stained using an acid-free double- staining solution to prevent the deterioration of calcified matrices in fragile larval skeletons. The proportion of bone and cartilage was quantified at each stage using a novel pixel-counting method. Growth and skeletal development were identical between treatments until the onset of metamorphosis (21 dph). However, from the metamorphosis stage, the growth and skeletal development rate was significantly faster in the intermediate treatment and significantly slower in the high treatment when compared to the control treatment. By 26 dph, A. japonicus reared in high pCO2 were, on average, 47.2% smaller than the control treatment, and the relative proportion of bone in the body was 45.3% lower in the high pCO2 treatment when compared with the control. In addition, none of the fish in the high pCO2 treatment survived after 26 dph. It appears that the combination of the increased energy requirements during metamorphosis and the increased energy cost associated with acid-base regulation may account for reduced growth, skeletogenesis and poor survival in high pCO2. Regardless of the driver, the results of this study suggest that the pCO2 levels predicted for the end of the century may have negative effects on the growth, skeletal development, and survival during metamorphosis.
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Effects of Pluronic F127 micelles as delivering agents on the vitro dark toxicity and photodynamic therapy activity of carboxy and pyrene substituted porphyrins
- Authors: Managa, Muthumuni , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234439 , vital:50196 , xlink:href="https://doi.org/10.1016/j.poly.2018.06.031"
- Description: Metal free, Zn and ClGa containing carboxyphenoxy and phenoxy groups (complexes 1) and pyrene groups (complexes 2) were synthesized and embedded into Pluronic F127 micelles (represented as F127). Dark toxicity and photodynamic therapy activities of the embedded porphyrins were successfully studied on MCF-7 breast cancer cells. Dark toxicity showed more than 80% cell viability for all complexes. It was found that 1-Zn + F127 showed better photodynamic therapy activity compared to 1-H2 + F127, and 1-ClGa + F127, corresponding to the high partition coefficient for the Zn porphyrin derivatives. The same applies to 2-Zn + F127 compared to 2-H2 + F127, 2-ClGa + F127. 1-ClGa and 1-Zn were also linked to Pluronic F127 silica nanoparticles. PDT activities for embedded 1-ClGa + F127 and 1-Zn + F127 were much higher than when linked to Pluronic silica nanoparticles (PluS NPs), showing the importance of loading of porphyrins into Pluronic F127 as a drug delivering agent rather than linking. PDT studies at the highest concentration of 60 µg/ml showed decrease in cell viability down to 15.9% for 2-Zn + F127. The Kp was determined in biphasic octanol and water system.
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Effects of the carboxylic acid substituents on the photophysical and nonlinear optical properties of asymmetrical Zn (II) phthalocyanines–quantum dots conjugates
- Authors: Mgidlana, Sithi , Oluwole, David O , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187662 , vital:44684 , xlink:href="https://doi.org/10.1080/24701556.2018.1503684"
- Description: This work reports on three asymmetrical Zn(II) phthalocyanines, namely: zinc(II) 3–(4-phenoxy)propanoic acid) phthalocyanine(1), zinc(II) 3–(4-phenoxy carboxylic acid) phthalocyanine (2) and zinc(II) 3–(4–oxy)phenoxy)acetic acid phthalocyanine (3) when covalently linked to glutathione(GSH) capped CdTe/ZnSe and CdTe/ZnSe/ZnO quantum dots (QDs). Of the Pc complexes alone, 1 afforded the highest triplet quantum yield (ΦT) value of 0.67 with corresponding largest nonlinear absorption coefficient (βeff) value of 14.0 cm/GW compared to 2 and 3. The conjugates afforded improved triplet quantum yield and nonlinear optical behavior in comparison to the Pc complexes alone.
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Electrocatalytic activity of a push-pull phthalocyanine in the presence of reduced and amino functionalized graphene quantum dots towards the electrooxidation of hydrazine
- Authors: Centane, Sixolile , Sekhosana, Kutloana E , Matshitse, Refilwe , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233456 , vital:50092 , xlink:href="https://doi.org/10.1016/j.jelechem.2018.05.005"
- Description: We report on the electrochemical behaviour of reduced graphene quantum dots (rGQDs) compared to amino functionalized graphene quantum dots (NH2GQDs). Reduction of the GQDs entails the elimination of the excessive carboxyl and hydrogen groups on the GQDs surface, thereby reducing the energy band gap. The energy band gap of graphene is directly proportional to the available oxygen atoms. The two GQD types were conjugated to a novel cobalt phthalocyanine (cobalt tris-(tert-butyl phenoxy)-mono-carboxyphenoxy phthalocyanine, CoPc) via covalent and nom-covalent interactions. The resulting conjugates were tested towards the electrooxidation of hydrazine. The conjugates are represented as rGQDs(π)CoPc, NH2(π)CoPc, rGQDs@CoPc and NH2GQDs@CoPc. The resulting conjugates were adsorbed onto a glassy carbon electrode using the drop and dry method. The lowest limit of detection (LOD) was obtained for rGQDs(π)CoPc.
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