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Preparation and Investigation of coumarin-based chemosensors towards sensing of ions using UV studies in aqueous systems
Humanity's unrelenting expansion has shown little regard for the environment, and this has resulted in tons of toxic heavy metal cations and anions being released into the environment through industrial, agricultural, electronic, and mining dumping. The release of these toxic heavy metals can cause diseases and sometimes lead to death, especially in third-world countries with low-income that reside in informal settlements, who suffer the most. Furthermore, the release of these toxins eventually finds their way back into the environment through bioaccumulation in fish, plants and animals. Although there is an ever need for the growth of these industries; low-cost, sensitive, selective, and organic-based sensors is a positive step forward in highlighting the need for environmental restoration and remediation, whilst striving to avoid unnecessary disease and death through this development. In this project, coumarin-based chemosensors for the detection of cationic and anionic species in aqueous and organic media are described. This project involves the synthesis of six different coumarin-based ether derivatives (E2-E5) and coumarin-based ester derivatives (H1-H2). FT-IR, 1H NMR and 13C NMR were used to confirm the structures of all sensors. The abilities of these novel compounds as chemosensors for detection of cations and anions were investigated using UV-vis analysis. These compounds displayed a favourable interaction with Fe2+ and Fe3+ ions with an increase in absorbance. Ether derivatives E2-E5 did not display any degree of selectivity or sensitivity towards the chosen anions. It was found that in the presence of FeCl2, sensors H1 and H2 displayed a degree of selectivities and further investigations were therefore carried out. From the titration experiments, the limit of detection, limit of quantification and association constants were determined. Job’s plot analyses were performed to determine the binding ratios, which was supported by Benesi-Hildebrand studies. The binding ratio between the sensors and metal cations during complexation was found to be 1:1. Reversibility studies were carried out using EDTA to determine whether the sensors could be reused. Molecular Modelling studies were used to determine the most preferred binding sites. Lastly, real-life application screenings were also run to determine if the sensors will be able to be used in real-life scenarios.Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 202
An evaluation of the monitoring and evaluation process of the scholar transport programme: a case of Amthole West Education District
Access to education is a constitutional right, calling for the state to institute reasonable measures to ensure every learner has access to education. The scholar transport programme was introduced to ensure access to education for learners who live far from school, particularly those living in rural areas. The study aimed to evaluate the processes that the scholar transport programme utilizes in the Amatole West Education District. Change theory served as the theoretical framework underpinning this qualitative study. Secondary data was collected and analyzed using thematic analysis. The study revealed that the Amatole West Education District employs several strategies, including stakeholder participation, route scrutiny, and safety checks. The research identified a lack of resources and capacity constraints as challenges to the Amatole West Education District encounter. The study recommends that the district enhance the competence of employees and other stakeholders with the necessary skills and knowledge to enable them to perform monitoring and evaluation(M&E) completely.Thesis (MPA) -- Faculty of Humanities, School of Governmental and Social Sciences, 202
Dancing with(in) possibilities: emerging public and convivial pedagogies for ecological citizenship
This research project explores ways in which ecological citizenship can be stimulated through collaborative public pedagogy and transgressive learning (t-learning) processes. This research identifies ‘places’ of innovation to cover sections that would usually be described in terms of ‘problem statement’, ‘research focus’, ‘intended outcomes / main contribution’ and ‘theory and methodology’. The Place of Worry is identified through the triple C Crisis (Covid, Capitalism and Climate-Change) which reveal the disconnect to the diverse ecologies (both social and natural) that sustain us. The Place of Possibility demonstrates that through ecological citizenship we can begin to absent absences (De Sousa Santos, 2016) and transform into an embodied response to the triple C crisis. The Place of Emergence transforms these possibilities into practice by demonstrating the place between the worry and the possibility allows for an emergence of a new kind of solution, referred to as the third space within this thesis. The Place of Process delves into the t-learning stories that emerged through research creation and works with iterative feedback and cycles of creation. The unfolding of this t-learning project is guided by the use of metaphor and symbolism as a figuration of macro- and microscopic interactions within these learning fields/ecosystems. Symbolic figuration and speculative metaphor are valuable in this thesis and in my own collaborative meaning-making endeavour as they offer translation protocols for when language fails to embody, the rich embodied experience of this form of learning. The embodiment of this work will help to create restorative care practices through transgressive learning (Lotz-Sisitka et al., 2016) and research creation (Manning, 2016). The study has a particular focus on the emergence of identities and onto-epistemological orientation within the social learning journey towards ecological citizenship and the various ways in which they can be embodied to enable public pedagogy.Thesis (MEd) -- Faculty of Education, Secondary and Post School Education, 202
Phthalocyanine-based bio-functional conjugates: photodynamic therapy and photoantimicrobial chemotherapeutic efficacy evaluation in-vitro
This thesis reports on the syntheses and characterisation of symmetrical and asymmetrical phthalocyanines (Pcs) with different ring substituents derived to form either cationic styryl pyridine, cationic styryl pyridine triphenylphosphonium (TPP+)-based, benzothiazole, cationic pyridyl-dihydrothiazole and other closely related groups. The starting Pc complex of the synthesised Pc derivatives was typically obtained through the cyclotetramerisation of a substituted phthalonitrile. Then, depending on the desired final complex, the desired complexes were synthesised through the Knoevenagel condensation, alkylation reaction, and Schiff base reaction. Furthermore, silica nanoparticles (SiNPs) were also used to encapsulate Pcs. Following aminopropyl triethoxysilane amino (APTES) functionalisation of the surface of the Pc@SiNPs-APTES, biomolecules such as gallic acid, folic acid, and ampicillin were covalently attached to the surface. Additionally, Pc@SiNPs-APTES is protonated with 1,3-propanesultone. The pair of synthesised asymmetric Pcs is attached to ciprofloxacin (CIP) via an amide bond. Different analytical methods were used to characterise the Pcs and their conjugates. The photophysics and photochemistry of the Pcs both by themselves and in their conjugate form when doped with SiNPs. The cationic Pcs were able to produce sufficient singlet oxygen on their own in most cases. This is explained by the Pcs greater solubility in water. Since singlet oxygen is produced from the triplet state, singlet oxygen quantum yield (Δ) values complement triplet quantum yield (T) values. Low Δ values could be attributed to ineffective energy transfer; screening effects may have prevented the excited triplet state of the Pcs from interacting with the ground state molecular oxygen, lowering the Δ values. In other instances, the Pcs' protection by the SiNPs could be credited with extending the triplet lifetime. The direct connection of Pcs with CIP increased the formation of T and Δ in ABSTRACT comparison to Pcs alone. Both in planktonic and biofilm form, the cationic Pcs and conjugates showed enhanced bacterial elimination. The Pcs and conjugates demonstrated significant activity in photodynamic therapy treatment (PDT) experiments at the tested doses. In both PDT and photodynamic antimicrobial chemotherapy (PACT) treatment, the cationic Pcs outperformed the neutral Pc in terms of biological activity.Thesis (PhD) -- Faculty of Science, Chemistry, 202
A battle of values: analysing the changing attitudes towards African refugees in Europe
Cosmopolitanism is a moral perspective that stresses the importance that every human being is an equal and ultimate unit of moral concern. These principles make cosmopolitanism more concerned for and accommodative towards outsiders to a political community. Against the abstraction and universalism of cosmopolitanism, communitarianism emphasizes the role communities play in shaping our individual identities and sees it as justified that the interests and well-being of community members receive priority over those of outsiders. Both these value systems are present in Europe. The question is about which direction the trend has moved in recent decades. This dissertation examines the changing values that inform attitudes toward African refugees in Europe to get at this issue. Have attitudes towards African refugees shifted in a cosmopolitan or a communitarian direction in recent decades? This dissertation examines newspaper articles from The Guardian between 1990 and 2022 to track changes in value. The analysis of these articles uncovered that communitarian values were the most prevalent and stayed the most prevalent from 1990 to 2022. These findings indicate that communitarian values are higher than cosmopolitan values regarding African refugees within the general European context. These findings add to the growing body of knowledge regarding attitude shifts, and they provide a timeline for value changes that can help predict future values and be used in future comparative studies.Thesis (MA) -- Faculty of Humanities, Political and International Studies, 202
Perceptions of registered counselors’ ability to process clients’ narrated dreams during counselling
Research related to South African registered counsellors (RCs) have yet to show how RCs incorporate dreamwork in their counselling sessions. Dreamwork has largely been relegated to the periphery of clinical psychological practice, posing a challenge as clients on other levels of counselling practice bring dream material to mental health practitioners often lacking confidence and competence to respond effectively to this material. Clients' discussion of dreams can be beneficial in the counselling process. However, there appears to be a gap in educational opportunities for practitioners to develop skills and competency in working with dreams. This study's objective was to contribute to the sparse research material in this area. A qualitative research approach with an exploratory design using semi-structured interviews was used to explore and understand the meaning RCs ascribed to their work with dreams and clients. Purposive sampling was used to recruit 5 participants. Social constructionism was used as a theoretical framework for understanding and interpreting the data, and the data was analysed using thematic analysis. This knowledge is geared towards providing insight into what extent university or college curriculum covered content related to dreams, dreamwork, dream theories, and dream models, and to what extent RC's training prepared them to provide essential primary psychological services related to distress arising from dreams. This research highlighted how RCs engaged and perceived their competency with dream material. This study also highlighted that RCs were interested in dreamwork training and believed it would enhance their confidence and effectiveness in working with dream material during their sessions.Thesis (MA) -- Faculty of Humanities, Psychology, 202
Identifying the factors that influence parents and caregivers to commit child maltreatment: systematic review
Child maltreatment, encompassing various forms of abuse and neglect, poses a significant global public health concern. This study provides a comprehensive examination of the multifaceted dimensions of child maltreatment, including physical, emotional, and sexual abuse, as well as neglect. The impact of maltreatment on the developing child is profound, resulting in a range of adverse physical and mental health outcomes, developmental delays, behavioural challenges, and social difficulties. The aim of this study was to comprehensively review and synthesise peer-reviewed research on the factors influencing parents and caregivers in committing child maltreatment. This systematic review identified the multifaceted factors influencing parents and caregivers to engage in child maltreatment. Using a social ecological framework, ten key themes emerged, namely poverty and lack of access to services, intergenerational transmission of abuse, childhood trauma, substance abuse, domestic violence, neighbourhood violence, cultural practices, social factors, children’s individual factors, and caregivers' mental health concerns. Personal history, caregiver’s mental health, substance abuse, poor awareness of self-protection, and gender emerged as significant individual-level contributors. Non biological caregivers and domestic violence were identified as relationship-level factors. At the community level, poverty, lack of access to services, unemployment, and neighbourhood violence were found to impact child maltreatment. Cultural values and the intergenerational transmission of abuse were reported as influential societal-level factors. The study underscores the complex interplay of personal, environmental, and cultural influences in child maltreatment, highlighting the need for comprehensive strategies to address this critical issue.Thesis (MA) -- Faculty of Humanities, Psychology, 202
Towards a possible future solution against Multidrug Resistance: An in silico exploration of the Multidrug and Toxic compound Extrusion (MATE) transporter proteins as potential antimicrobial drug targets
The rise of multidrug resistance (MDR) has become a pressing global issue, hindering the treatment of cancers and infectious diseases, and imposing a burden on healthcare systems and the economy. The Multidrug and Toxic compound Extrusion (MATE) superfamily of membrane efflux transporters is one of the key players contributing to MDR due to their ability to export a wide range of cationic and hydrophilic xenobiotics, including treatment drugs, from cells, diminishing their efficacy. Targeting MATE transporters holds great promise in achieving some cellular control over MDR, but first, a deeper understanding of their structure-function-dynamics link is required. This study aimed to explore the MATE transporters as potential antimicrobial drug targets using a two-fold in silico approach. First, virtual screening of compounds from the South African Natural Compounds Database (SANCDB) was performed to identify prospective lead inhibitory compounds against the MATE transporters using molecular docking, and top hits were selected based on their binding energy and interaction with the active site on the N-lobe of the protein. Second, to investigate the molecular-level dynamics of their extrusion mechanism, the MATE transporter structures were embedded in a POPC membrane bilayer using the CHARMM-GUI online tool and then subjected to MD simulations for 100 ns with the CHARMM 36m force field using GROMACS. The resulting trajectories were evaluated using three standard metrics – RMSD, RMSF, and Rg; significant global structural changes were observed and key functional regions in both membrane- and non-membrane transmembrane (TM) segments were identified, containing more dynamic and flexible residues than other regions. Furthermore, the MATE transporters showed more of a loosely-packed structure, providing flexibility to allow for conformational switching during their substrate-transport cycle, which is typical for proteins whose secondary structures are composed of all α-helices. The scope of this study lied in the preliminary stages of the computer-aided drug design process, and provided insights that can be used to guide the development of strategies aimed at regulating or inhibiting the function of the MATE transporters, offering a possible future solution to the growing challenge of MDR.Thesis (MSc) -- Faculty of Science, Biochemistry and Microbiology, 202
High-altitude temporary systems and macroinvertebrate composition in La Nina cycle, Maloti-Drakensberg
The Maloti-Drakensberg Mountain is an important water catchment area for South Africa and Lesotho. It is rich in biodiversity in terms of endemic flora and fauna and has a high density of temporary wetlands in the form of Afromontane tarns and rock pools. There is, however, limited information on the distribution of macroinvertebrates in these ecosystems and environmental factors that drives their composition. To that end, this study investigated macroinvertebrate diversity and the effect of environmental factors on community assemblage in the Maloti-Drakensberg Mountain temporary wetlands, specifically tarns and rock pools. The main aims were to describe the abundance, diversity, and distribution of macroinvertebrates in temporary wetlands in the Maloti-Drakensberg Mountain. Furthermore, it aimed to investigate the effect of environmental variables on habitat structuring, spatial variations, and macroinvertebrate community composition in tarns and rockpools in the Maloti-Drakensberg Mountain. Seventy temporary wetlands (29 tarns and 41 rock pools) were surveyed over a once-off sampling (3 March – 7 April 2022). The wetlands were from 3 provinces including Eastern Cape, Free State, and KwaZulu-Natal. 15278 individual macroinvertebrates from 13 orders, 35 families, and 46 genera were collected and identified. Species accumulation curves incorporating both tarns and rock pools showed that observed results were significantly lower than Chao 1 and Chao 2 estimates meaning that the sampled sites were not enough to provide a comprehensive picture of the biodiversity in the region. This was also observed for rock pools when the temporary wetlands were analysed separately, however, the Chao 1 and Chao 2 values for tarns were almost equal to the observed values implying that sampled sites were enough to give a detailed picture of macroinvertebrate composition in tarns. Tarns and rock pools were significantly different in terms of species richness and Shannon-Wiener diversity index but showed no significant differences for relative abundance and Pielou’s evenness. Of the 35 families identified, 19 were considered core taxa with Dytiscidae and Corixidae being the most dominant. Additionally, there was moderate Nestedness metric based on Overlap and Decreasing Fill (NODF) value of 33.05369, with 32 out of 35 families being idiosyncratic. Predators were the dominant feeding group with omnivores being the least common. Non-Metric multi-Dimensional Scaling (NMDS) and PERMANOVA results showed that tarns and rock pools supported distinctly different macroinvertebrate communities per wetland type and location respectively. Physicochemically, tarns and rock pools were significantly different in terms of water temperature, depth, area, and chlorophyll-a concentration with tarns exhibiting higher values. Temporary wetlands in the sampled localities differed in terms of pH, EC, DO, water temperature, altitude, and phosphate. Principal Component Analysis showed that tarns were positively associated with area and depth whereas rock pools with phosphate. Akaike’s Information Criterion (AICc) selection showed that area, pH, and water temperature were significantly influencing community assemblage in temporary wetlands. Furthermore, area significantly influenced all four measured biodiversity indices: relative abundance, species richness, Pielou’s evenness and Shannon-Wiener Index, with water temperature also influencing relative abundance and altitude, species richness. Overall, the species composition showed that the sites were sampled later in the hydroperiod as evidenced by the dominance of active dispersers. The extended distribution of Prosthetops gladiator in the Eastern Cape highlights the need for extensive surveys to provide valuable insight into the distribution patterns of macroinvertebrates in the region. Furthermore, the interplay between physicochemical variables and biodiversity indices emphasized area, water temperature and pH as significant factors. However, their limited explanatory power suggests that obscure factors also influence the diversity cementing the need for further exploration of these enigmatic systems. Taxonomic challenges, especially regarding large branchiopods, hindered precise species distribution and conservation status determination. This study is the first to provide a comprehensive list of macroinvertebrates from temporary wetlands in the Maloti-Drakensberg Mountain. These results establish a valuable baseline for future biological monitoring studies, particularly in assessing species composition and responses to anthropogenic activities. It is a timeous study considering the sensitivity of these systems to climate change as they act as sentinel sites hence the need for foundational data on which to make future projections.Thesis (MSc) -- Faculty of Science, Zoology and Entomology, 202
The private collection: aura, the cult of celebrity and, the construct of value in saleable works of art
A tenet of the twenty-first century is the monetisation of everything due to commercialisation. The effects of this commercialisation have crept into every aspect of our lives, and although in the art world it has mostly been underhanded in its adoption, the traces of commercialisations touch are still evident in its functioning. Due to this underhandedness there hasn't been much thought put into what 'the monetisation of everything' truly implies for the industry, or how the value of the art object devoted to commercialisation may look like. The Private Collection (exhibition title of the practical component for submission in MFA completion) addresses the concept of object value and, more specifically, how that value is created within the art world through mechanisms of commercialisation that include celebrity cult, functioning of possession (through collecting), and taste. Research into Walter Benjamin's theory of the authenticity of the work of art, and in particular his concept of "aura," has helped inform the creation of a marketing strategy propelled by value driven mechanisms found within the Art Market for The Private Collection. Particular emphasis is placed on how brand value drives sales in this thesis. Thus, The Private Collection: Aura, the Cult of Celebrity, and the Construct of Value in Saleable Works of Art, defines The Private Collection as a tailored system built expressly for engagement with economic forces inside the art industry. As a result, the position of this study is based on the marketability of the object through particular driving forces that have seeped into the value system of the saleable work of art. The position of this thesis is that in this commercialist system, driving forces of value can be sustained within instances of the multiple. The project additionally supports this in maintaining that interaction from a fine art perspective would be limited if restricted to orthodox approaches (a gallery showing, and one print works), which is why a more economically interactive approach (e-commerce) was decided on for the exhibition component. The Private Collection offers an observation that the worth of a saleable work of art has become a warped representation of the commercial context we find ourselves in and that value is only awarded through particular kingmakers of the system. The practical component of this submission can be viewed online by clicking the image below. Please note that the website is not optimised for phone or tablet use, please instead view it on a computer (preferably a desktop) in full screen mode.Thesis (MFA) -- Faculty of Humanities, Fine Art, 202