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The electrocatalytic activity of metallophthalocyanines and their conjugates with carbon nanomaterials and metal tungstate nanoparticles
Get PDFIn this dissertation, seventeen phthalocyanine complexes were synthesised. Of these, only four are known and have been published. These complexes were synthesised using the conventional statistical condensation method that involves refluxing the phthalonitrile(s) (4-((1,3-bis(dimethylamino)propan-2-yl)oxy)phthalonitrile, 4-(4-carboxyphenoxy)phthalonitrile, 4-(4-acetylphenoxy)phthalonitrile, dimethyl 5-(3,4-dicyanophenoxy)-isophthalate, 4-(4-(tert-butyl)phenoxy)phthalonitrile, 5-phenoxylpicolinic acid phthalonitrile 4-(4-formylphenoxy) phthalonitrile, and 4-(4-(3-oxo-3-phenylprop-1-enyl) phenoxy) phthalonitrile) with the metal salt and 1,8-diazabicyclo[5.4.0]undecane as a catalyst in a high-temperature solvent. And thereafter (when necessary), isolation and purification of the target compounds were achieved through the use of silica column chromatography. These compounds were characterised using various analytical techniques such as; ultraviolet-visible absorption, mass spectroscopy, and Fourier transform infrared spectra and elemental analysis. These techniques proved that the complexes were successfully synthesised and isolated as pure compounds. Carbon-based (graphene quantum dots and nitrogen-doped graphene quantum dots) and metal oxide (bismuth tungsten oxide and nickel tungsten oxide) nanomaterials were synthesised. Together with the purchased single-walled carbon nanotubes, these nanomaterials were conjugated to some of the MPc complexes via non-covalent (carbon-based nanomaterials) and covalent (metal oxides) linkage forming hybrid materials. These nanomaterials and hybrids were characterised using various analytical methods (ultraviolet-visible absorption, X-ray diffraction, Raman spectroscopy, thermographic analysis, and dynamic light scattering). Nanomaterials were utilised herein to determine their effect on the properties of MPc complexes and provide a synergistic effect in the hope of enhancing these properties. All complexes synthesised in this work (MPcs, nanomaterials and hybrids) were employed as electrocatalysts in electrochemical sensing. These electrocatalysts were embedded onto the glassy carbon electrode via an adsorption method known as drop-casting. The modified electrode surfaces were characterised using cyclic voltammetry, electrochemical impedance spectroscopy and scanning electrochemical microscopy to determine various electrochemical parameters. These electrocatalysts were used in the detection of either nitrite, catechol and/or dopamine. The detection limits, sensitivities, kinetics and catalytic constants were among other parameters determined for each electrocatalyst. These electrocatalysts proved to be stable electrocatalysts that could potentially be used for practical applications. The determined parameters were comparable and sometimes better than those obtained in literature.Thesis (PhD) -- Faculty of Science, Chemistry, 202
Exploring rural youth livelihood opportunities: a case study of a youth centre in Bizana
Get PDFThroughout South Africa, youth that are not in Education, Employment, or Training (NEET) continue to face many socio-economic challenges, including unemployment. Bizana, a small rural town in the Eastern Cape, is no exception. This study explores rural youth livelihood opportunities for youth NEET in Bizana. There is limited research done to understand the role of youth centres in providing accessing to rural youth livelihood opportunities. As a result, this study sought to understand the role of youth centres in re-integrating youth NEET into the labour market, as well as into education and training institutions. It utilizes the case study of the Bizana Love Life youth centre by looking at the programmes they offer, and whether they enhance livelihood opportunities for youth NEET. The Sustainable Livelihoods Approach (SLA) was used as a theoretical lens in understanding rural youth livelihood opportunities for youth NEET in Bizana, by identifying the challenges they face and the assets they use to enhance their livelihoods. Against this backdrop, the study adopted a qualitative research approach and an explorative case study design and was supplemented by purposive and snowball sampling methods. Data was obtained using semi-structured interviews with twelve youth NEET participants who are part of the programmes of the youth centre, and two staff members of the youth centre. Findings were analysed using open coding and thematic analysis in line with the objectives of the study. The findings of the study revealed that in attempting to gain employment, extended family support, parenthood, financial reasons, household chores, poor academic performance and lack of work experience were some of the challenges facing rural youth NEET in Bizana. The findings indicate that a combination of human and social capital can be used to support youth NEET in gaining confidence and in preparing them for the workplace. With these findings, the study indicates the need to strengthen existing youth programmes that cater for youth NEET, who are the most vulnerable in the labour market, through skills development and broadening of their social networks. As a policy recommendation, the national and provincial government must work with youth centres and other stakeholders to establish policies that cater for the development of youth NEET.Thesis (MSocSci) -- Faculty of Humanities, Sociology, 202
Towards a better understanding of small-scale fishing decisions and their consequences in Northern Mozambique
Get PDFThis study investigates the relationship between the interacting social and ecological systems within the Pemba Bay fishery, in Northern Mozambique, as mediated by fishing decisions. All ecosystems in the world are affected by human behaviours in some way. In many cases, human effects on ecosystems are detrimental to many other species and can cause shifts in the entire system. In fisheries, the connections between human behaviours and ecosystems are obvious, as fishers extract wild populations of marine species. Human behavioural plasticity and sometimes rapid cultural evolution allow human behaviours to change and adapt faster than many other species can respond which often allows fishers to overexploit marine ecosystems. Many fisheries in the world are fully, or over exploited. Managing these fisheries often focuses on changing those highly adaptable human behaviours. Fishers’ motivations for making different fishing decisions as well as attitudes towards the fishery can be used to understand human interactions with ecosystems when the dependence between the two is direct, as well as allowing managers to tailor interventions that account for fishers’ motivations and attitudes. Most fisheries’ management projects assume that behaviours are motivated by profit maximization. This study investigates this assumption by comparing the compatibility of interview responses and fishing behaviours with rational actor theory, which assumes profit maximization is the only goal. Responses are also compared with prospect theory, which emphasizes reliability of outcomes; descriptive norms, which focuses on social interactions; habitual behaviour, which assumes most decision are automatic based on habit; and theory of planned behaviour, which allows attitudes to be shaped by economic or non-economic motivations, as well as peer opinion and incorporates perceived behavioural control in making decisions. These behavioural theories span a variety of potential fisher motivations which could affect fishing decisions. The study then investigates the state of the social and ecological systems which have resulted, at least in part, from those fishing decisions, and makes recommendations on possible interventions to improve the system based on better understanding of fishers’ attitudes and motivations. The study tests the hypothesis that fishers are motivated primarily by profit maximization and, therefore, rational actor theory is most compatible with fishers’ stated motivations for fishing, or alternatively, that one of the other behavioural theories better explains fisher responses. This section used categorized interview responses based on their agreement, or not, with assumed responses if a particular behavioural theory were compatible. The results indicate that four of the five theories are most compatible with responses for at least one fisher, but that the theory of planned behaviour is the most consistent with the data overall, not rational actor theory. Specifically, fishers seem concerned with behavioural control as well as some non-catch related characteristics of the fishery, such as collective action and sustainability. The second hypothesis is that prospect theory is more compatible with current fishing behaviours than rational actor theory. Prospect theory states that people prefer more reliable outcomes, even if slightly less profitable, than outcomes which are more profitable on average, but also more variable. This section used catch data, and changes in relative use of different fishing methods to address this hypothesis. This hypothesis is confirmed for some aspects of fishery data, but not all. Fishers prefer methods which are more reliable and these methods are increasing in relative use. However, neither catch value nor reliability increases fishers’ opinions of their fishing method, but fisher characteristics which increase options do. This again indicates that behavioural control is important in determining fishers’ attitudes towards fishing. The third question addresses the social system within the fishery. It investigates whether fishing in Pemba Bay is a chosen profession or a livelihood of desperation from the poorest individuals. The study hypothesizes that fishers are as well-off as their non-fishing neighbours, and fishers who use more reliable or profitable methods are better off than those using less reliable/profitable methods and, as such, are more committed to fishing as a way of life. This section used fisher interview responses and household surveys to compare subjective and material wellbeing of fishers and non-fishers around Pemba Bay. The first part of the hypothesis is partly supported. Fishers using most methods have material standards of living comparable to non-fishers. However, they report lower subjective well-beings. Most measures of wellbeing are not affected by the reliability or profitability of the fishing method used, which does not support the second part of the hypothesis. Additionally, fishers using more profitable or reliable methods do not indicate more commitment to fishing as a way of life. The fourth and final section investigates the marine ecosystem. Based on conversations with fishers and local researchers, it is assumed that the Pemba fishery is overexploited. As such, the study hypothesizes that marine biomass, individual size of marine species, and functional diversity are lower in Pemba Bay than in other sites around Northern Mozambique, Vamizi Island, Situ Island, and Nuarro, due to high fishing pressure, and that direct removal of species by fishing has a dominant effect. This final section used baited remote underwater videos (BRUVs) to compare species composition and indices of abundance from the different locations. Again, there is support for part of this hypothesis. Marine species biomass and sizes are lower in Pemba Bay than other sites in Northern Mozambique; however, functional diversity is not different. In these data, changes in biomass and size are not correlated with amount of catch, so direct removal by fishing may not be the dominant source of change in the Pemba fishery. Together, these data indicate that the Pemba fishery may be unsustainable based on social and ecological indications. The importance of behavioural control in understanding fishing decisions indicates that any interventions to mitigate problems in the fishery will need to work with fishers to increase empowerment and allow experimentation to find locally relevant solutions to problems.Thesis (PhD) -- Faculty of Science, Ichthyology and Fisheries Science, 202
A Comparison of Mitochondrial Heat Shock Protein 70 and Hsp70 Escort Protein 1 Orthologues from Trypanosoma brucei and Homo sapiens
Get PDFThe causative agent of African trypanosomiasis, Trypanosoma brucei (T. brucei), has an expanded retinue of specialized heat shock proteins, which have been identified as crucial to the progression of the disease. These play a central role in disease progression and transmission through their involvement in cell-cycle pathways which bring about cell-cycle arrest and differentiation. Hsp70 proteins are essential for the maintenance of proteostasis in the cell. Mitochondrial Hsp70 (mtHsp70) is a highly conserved molecular chaperone required for both the translocation of nuclear encoded proteins across the two mitochondrial membranes and the subsequent folding of proteins in the matrix. The T. brucei genome encodes three copies of mtHsp70 which are 100% identical. MtHsp70 self-aggregates, a property unique to this isoform, and an Hsp70 escort protein (Hep1) is required to maintain the molecular chaperone in a soluble, functional state. This study aimed to compare the solubilizing interaction of Hep1 from T. brucei and Homo sapiens (H. sapien). The recently introduced Alphafold program was used to analyze the structures of mtHsp70 and Hep1 proteins and allowed observations of structures unavailable to other modelling techniques. The GVFEV motif found in the ATPase domain of mtHsp70s interacted with the linker region, resulting in aggregation, the Alphafold models produced indicated that the replacement of the lysine (K) residue within the KTFEV motif of DnaK (prokaryotic Hsp70) with Glycine (G), may abrogate bond formation between the motif and a region between lobe I and II of the ATPase domain. This may facilitate the aggregation reaction of mtHsp70 orthologues and provides a residue of interest for future studies. Both TbHep1 and HsHep1 reduced the thermal aggregation of TbmtHsp70 and mortalin (H. sapien mtHsp70) respectively, however, TbHep1 was ~ 15 % less effective than HsHep1 at higher concentrations (4 uM). TbHep1 itself appeared to be aggregation-prone when under conditions of thermal stress, Alphafold models suggest this may be due to an N-terminal α- helical structure not present in HsHep1. These results indicate that TbHep1 is functionally similar to HsHep1, however, the orthologue may operate in a unique manner which requires further investigation.Thesis (MSc) -- Faculty of Science, Biotechnology Innovation Centre, 202
Lessons learned from the translation of the Internalised Stigma of Mental Illness (ISMI) scale into isiXhosa for use with South African Xhosa people with schizophrenia
Get PDFInternalised stigma is highly prevalent among people with mental illness. This is concerning because internalised stigma is often associated with negative consequences affecting individuals’ personal, familial, social, and overall wellbeing, employment opportunities and recovery. Currently, there is no psychometrically validated instrument to measure internalised stigma among Xhosa people in their home language. Our study aimed to translate the Internalised Stigma of Mental Illness (ISMI) scale into isiXhosa. Following WHO guidelines, the ISMI scale was translated using a five-stage translation design which included (i) forward-translation, (ii) back-translation, (iii) committee approach, (iv) quantitative piloting, and (v) qualitative piloting using cognitive interviews. The ISMI isiXhosa version (ISMI-X) underwent psychometric testing to establish utility, within-scale validity, convergent, divergent, and content validity (assessed using frequency of endorsements and cognitive interviewing) with n = 65 Xhosa people with schizophrenia. The resultant ISMI-X scale demonstrated good psychometric utility, internal consistency for the overall scale (α = .90) and most subscales (α > .70, except the Stigma Resistance subscale where α = .57), convergent validity between the ISMI Discrimination Experiences subscale and the Discrimination and Stigma (DISC) scale's Treated Unfairly subscale (r = .34, p = .03) and divergent validity between the ISMI Stigma Resistance and DISC Treated Unfairly subscales (r = .13, p = .49). But more importantly the study provides valuable insights into strengths and limitations of the present translation design. Specifically, validation methods such as assessing frequency of endorsements of scale items and using cognitive interviewing to establish conceptual clarity and relevance of items may be useful in small piloting sample sizes
Monitoring strategies used for teaching and learning in selected scondary schoolsof OR Thambo Inland Education District, Eastern Cape Provice, South Africa
Get PDFThis study was meant to investigate monitoring strategies used for teaching and learning in selected secondary schools of OR Tambo Inland Education District in Eastern Cape Province of South Africa. The study mainly concentrated on collecting the analysed data from principals, deputy principals and heads of departments of secondary schools of Qumbu magisterial district on the basis of my proximity to their schools. A case study research design was adopted as only principals, deputy principals and HODs officially employed by the Department of Education to teach in geographically located secondary schools in Qumbu magisterial district were used as subjects to collect data. The qualitative research approach was employed in this study. A sample of 15 participants who were chosen using purposive sampling were interviewed face-to-face adopting semi-structured interviews to gather data for this study. The findings supported SMTs' use of monitoring curriculum implementation methodologies, but their actual implementation was characterised by a lack of rigour and decisiveness. Evidently, a number of contextual circumstances influenced to what extent the methods that had been decided upon were carried out. It emerged that in some SMTs’ strategies to manage and monitor the quality of teaching and learning in their secondary schools, teacher unions disrupts such systems. This implies that the teacher unions play a detrimental role in limiting effective intervention strategies by management. As long as teacher unions plays a powerful role in tying the hands of management in quality control oversight, management will find it very difficult to make inroads into improving commitment by teachers and progress of learners. The Department of Basic Education and government need to review and revise the powers of teacher unions.Thesis (Masters) -- Faculty of Education, 202
The moderating effect of socioeconomic factors on the relationship between financial inclusion and poverty among South African vulnerable households
Get PDFVulnerable households are often excluded from the formal financial sector, subsequently experiencing more poverty. Vulnerable households are those that face higher chances of experiencing higher levels of poverty due to their socioeconomic factors. This study aimed to determine the moderating effect of socioeconomic factors on the relationship between financial inclusion and poverty among South African vulnerable households. Poverty is the involuntary lack of monetary and other resources that can afford households with basic human needs and a decent standard of living above a chosen poverty measure. This study measured poverty using a multidimensional measure that incorporated a household’s deprivation of health, education and a decent standard of living. Financial inclusion refers to a process of incorporating vulnerable households into the formal financial sector by ensuring that they receive timely and adequate access to regulated financial products at an affordable price, regardless of their socioeconomic status. This study measured financial inclusion multidimensionally using access to four basic regulated financial products. Socioeconomic factors included gender, race, first or home language, age, the highest level and many more factors. This study was supported by theoretical framework of the vulnerable group theory of financial inclusion, financial development theory, the credit rationing theory and the public goods theory of financial inclusion. The study adopted a quantitative research design. The study used existing data from the FinMark FinScope 2016 South Africa database, which collected data on households’ demographics and their ownership of financial products. Using a closed-ended questionnaire, FinMark FinScope collected the data across South Africa through a multi-probability sampling technique. The final database used in this study after data cleaning contained a sample of 2759 households. The study used descriptive statistics, Pearson’s product-moment correlation, ANOVA and Multiple regression to investigate the factors of the study. The results of the study found a statistically significant relationship between financial inclusion and vulnerable households. The results also found a statistically significant relationship between poverty and vulnerable households. The results further showed a statistically significant negative relationship between financial inclusion and poverty. Lastly, the study found that only socioeconomic factors such as marital status, age as it relates to children and old people moderating effect on the relationship between financial inclusion and poverty among South African vulnerable households. Subsequently, it was concluded that vulnerable households experienced higher levels of poverty in South Africa, and these vulnerable households were less financially included in South Africa. Additionally, it was found that increasing vulnerable households’ access to all regulated financial products could help decrease their poverty levels. The study made several recommendations, which included inter-alia that formal financial institutions design products that specifically meet the needs of vulnerable households. This study also recommended that banks play a central role in facilitating vulnerable households’ affordability of health in South Africa (e.g., offering affordable healthcare products to vulnerable households). Theoretically, this study contributed to the body of literature using multidimensional financial inclusion and poverty, as well as determining the moderating effect of socioeconomic factors. Practically, this study provided insights to the banks on how to develop their products to meet the needs of vulnerable households, help alleviate poverty, and increase the banks’ market into previously unbanked or underbanked segments of the population of South Africa.Thesis (MCom) -- Faculty of Commerce, Accounting, 202
“How do you feel about the abortion?”: pre-termination of pregnancy counselling in the public health sector in the Eastern Cape
Get PDFPre-abortion counselling, as an aspect of abortion provision, has received growing research interest in various contexts. Much of the research has primarily focused on whether abortion counselling takes place, the experiences of women and/or counsellors (usually through retrospective interviews and surveys), and the content discussed during the counselling session (often policy regulated). Such research has proven vital to addressing the various reproductive issues facing women seeking an abortion worldwide. However, little research has focused on how pre-abortion counselling as an everyday institutional practice is conducted at a conversational level in the medical setting. By drawing on both conversation analysis and discursive psychology, this study explored how pre-abortion counselling was conducted in the public health sector in South Africa. The study involved recording the conversation during pre-abortion counselling and analysing it in terms of its content, in particular, the discourses drawn on by all parties involved, and its structure and delivery. The data were collected from three public hospitals in the Eastern Cape of South Africa and involved the audio recording of pre-abortion counselling sessions as part of abortion services. In total, 28 counselling sessions were recorded: 21 were individual sessions, and 7 were group counselling sessions. At two of the sites, counselling was conducted by registered midwives who worked at the hospital. At one site, an external Christian organisation volunteered trained counsellors to counsel women at the hospital free of charge. Using conversation analysis, counselling sessions were analysed in terms of the main projects. Seven key projects were identified: (1) Context setting, (2) History taking, (3) Establishing reason for abortion, (4) Presenting options, (5) Providing procedural information, (6) Obtaining verbal informed consent, and (7) Discussion of family planning. Each project is explored in terms of what discourses and subject positions featured when speakers were orienting to a specific project. This process highlighted how the conversational projects and their respective goals enable the deployment of certain problematic discourses and interactive/reflexive positionings. Discourse analysis revealed a clustering of discourses around two central themes. In the first clustering, the discourses were primarily used to discuss the (1) medically related issues underpinning the abortion procedure [medical discourse, responsibilization discourse, risk discourse, and discourse of support]. Talk using these discourses positioned women as patients needing medical intervention, responsibilised women for conceiving, playing an active role in their termination, and navigating all the psychological and physical risks “associated” with abortion. The discourse of support illustrates how support was spoken about in the interaction whereby patients were constructed as subjects who required support and nurses/counsellors as the ones who offered the support. In the second clustering, the discourses (2) focused on women and the foetus. These discourses [reproductive choice, religious, pronatalist, and foetal personhood discourses] positioned women as being responsible for making a choice regarding their pregnancy and the consequences that may result. In addition, a religious discourse coupled with a pronatalist discourse was used to construct the pregnancy and motherhood as desirable and part of “God’s plan”, whereas the foetus was spoken about as a “gift from God”. The foetal personhood discourse was used to construct the foetus as a living and functional human. This research provides evidence of how abortion counselling is problematic at various levels. At a practical level, there is a lack of standardisation in the delivery of abortion counselling (e.g., variation in key projects, where the counselling is mandated, time taken, nurse/counsellor training, content and format – group vs. individual counselling). At a discursive level, the use of certain discourses works to render the counselling directive through : (1) awfulizing abortion by providing misinformation about the abortion procedure, foetus and post-abortion psychological distress, (2) chastising and responsibilising women for conceiving, (3) constructing abortion as immoral, the ending of life and not in line with God’s plan, (4) constructing parenthood as the preferred choice, (5) delegitimising abortion as a resolution for pregnancy when compared to the other options (e.g., parenting or adoption), and finally (6) providing counselling that does not take into account the broader socio-political contexts. Recommendations for future research are put forward, and a call to move to a reparative justice framework is made by highlighting how it can be used to identify and understand reproductive injustices as they occur along four intersecting dimensions: (1) Individual material, (2) Collective material, (3) Individual symbolic, and (4) Collective symbolic.Thesis (PhD) -- Faculty of Humanities, Psychology, 202
A qualitative systematic review exploring online learning experiences among university students during Covid-19: An African Context
Get PDFThe sudden and immediate transition to online learning during the COVID-19 pandemic brought forth unprecedented challenges, particularly within the education sector. In Africa, this shift was necessitated by the need to safeguard lives and preserve the academic year. However, the absence of adequate contextual consideration introduced additional complexities, influencing how students in the African context navigated their learning experiences during this unique time.This study aimed to comprehensively synthesize the online learning experiences of university students in Africa amid the COVID-19 pandemic and evaluate the influence of these experiences on academic performance. Drawing from the systematic review protocol proposed by Hemingway and Brereton, seven (7) qualitative research articles were rigorously selected based on predefined inclusion criteria and meticulously examined.Thematic analysis of the chosen articles revealed two overarching themes. The first, "Emotional Distress," encapsulated students' experiences of anxiety, depressive emotions, and anger. Contributing factors included limited interaction opportunities, a sense of isolation, insufficient online learning resources, inflexible course structures, and non-conducive learning environments. The second overarching theme, "Growth," encompassed improvements in grades and enhanced self-directed learning abilities.These findings hold significant implications for the enhancement of online learning experiences in Africa. To address the challenges associated with emotional distress and foster growth, we propose the following recommendations: increased focus on social interaction and support mechanisms, equitable access to online resources, flexible course structures, and fostering conducive learning environments.Thesis (MA) -- Faculty of Social Sciences and Humanities, 202
Persistent effects of historical sea levels on the population structure of a temporary wetland copepod
Get PDFTemporary wetland ecosystems are common in arid and semi‐arid envi-ronments, and are inhabited by diverse invertebrate communities. Little is known about the dynamics of genetic connectivity in the geograph-ically scattered populations of these wetland specialists. The current study investigated the spatial genetic structure and dispersal history of a recently described calanoid copepod, Lovenula raynerae, reported from temporary wetlands in the Eastern Cape province of South Africa. We tested whether the species represents a single, well‐connected population or comprises different regional genetic groups, some of which may be rare or endangered