Electronic Theses and Dissertations (PhDs)

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A study of the support effect of carbon dots-derived graphene-like sheets on the autoreduction of cobalt nanoparticles for Fischer–Tropsch synthesis
(2022) Mokoloko, Lerato Lydia
The aim of this study was to synthesize and characterize carbon dots (CDs) and to use them as a support material for cobalt (Co) based Fischer-Tropsch synthesis (FTS) reactions. The CDs were chosen for this study due to their small size (< 10 nm), easy surface functionalization and synthesis. The small size of the CDs was required for the study of inverse catalyst support effects. An inverse supported catalyst (in this case, the Co/CDs catalyst) refers to the dispersion of a support material that has a small size (d < 5 nm) onto the surface of a metal catalyst with a similar small size (d > 8 nm). The synthesis of this proposed catalyst was successful. FTS studies on the Co ‘supported’ CDs were attempted. Extremely poor FT activity was observed. Post analysis of the catalyst revealed that the CDs did not retain their quasi-spherical and small particle size morphology under the FTS reaction conditions (temperature 220 °C, 10 bar P; H2:CO ratio = 2:1). Instead, upon exposure to a heat treatment, the CDs were transformed into layered structures with a unique resemblance to graphene-based nanosheets (GNSs). This transformation impacted on the use of these catalysts in the FTS reaction. However, this result indicated an unusual transformation of the CDs into another carbon shape. In light of the fascinating transformation phenomenon, annealing studies were then conducted to investigate the effect of annealing temperatures on the CDs structural changes. The CDs (average d= ~ 2.5 nm) used in this study were obtained from the microwave-assisted carbonization of L-ascorbic acid and subjected to a heat treatment (i.e. annealing) at temperatures between 200 and 700 ℃ in a horizontal CVD apparatus under an inert nitrogen gas. It was observed that annealing transformed the CDs from 0-D qausi-spherical nanoparticles to 3- D multi-layered carbons (at 300-600 ℃) and finally 2-D layered materials (at 700 ℃). Furthermore, annealing at 700 ℃ yielded a 2-D single-layered material with comparable properties to traditionally reduced graphene oxide (rGO). A wide range of characterization techniques were used to gain an insight into the physicochemical properties of these novel CDs-derived allotropes as well as to rationalize their mechanism of formation. After evaluating the properties of these materials, it was clear that the surface oxygen functional groups, observed from XPS, 13C NMR and other studies, were responsible for the CDs to rGO transformation. It was proposed that the CDs are assembled to form rGO (and other CDs-rGO derivatives) by either the Ostwald ripening (in which the carbons agglomerated via a gas phase) or a solid phase reaction (involving reaction of CD edges). To further investigate the effect of annealing on the evolution of CDs to layered carbon structures, N-doped CDs (or NCDs) were also studied. The method used to make the pristine CDs was modified by incorporating urea as a nitrogen source to make the NCDs. Annealing the NCDs at temperatures between 200 and 700 ℃ also transformed the quasi-spherical NCDs (average d = ~ 4.1 nm) to multi-layered carbon sheets at temperature as low as 200 ℃. The CD transformation was also associated with the loss of surface functional groups, with % O and N contents of ca. 17 and 16 % (pristine NCDs) being reduced to ca. 8 and 7 % for NCDs annealed at 700 ℃. A similar mechanism for the formation of these N-doped layered carbon structures by annealing was also proposed here. For these samples, it was also observed that the N-bonds, especially the sp3 type nitrogen bonds found on the edges of the NCDs, also took part in the coalescence of the NCDs to give the layered materials. XPS data suggested that in the process, these sp3 type nitrogen bonds were transformed into sp2 pyrrolic-N, pyridinic-N and GraphiticN groups. The annealed CDs products were used to support Co (called Co3O4/T250, Co3O4/T400 and Co3O4/T700 where T is the temperature at which the CDs were annealed) for use in FT studies. Studies were conducted to evaluate the effect Co hydrogen reduction temperatures verses autoreduction temperature, catalyst thermal stability and performance in the FTS reaction at 220 °C (10 bar P; H2:CO ratio = 2:1). Upon investigation of the reduction behaviour of the Co/CDs derivative catalysts using in situ PXRD, it was found that these materials can successfully facilitate autoreduction of Co3O4 to Co face-centered-cubic (fcc) at temperatures > 400 ℃ by a reduction pathway similar to that observed using conventional H2 reduction conditions. As expected, the reduction under H2 took place at a lower activation temperature (> 250 ℃) than the autoreduction process. It was also noted that these novel carbon support derived from CDs gave reduced FTS performance compared to the unsupported Co, especially towards C5+ yields (< 30 % for all Co supported catalysts). These novel CDs-derived allotropes were found to have limited use as supports in Co-based FTS, due to Co agglomeration. These NCDs-derived allotropes (annealed at 200 ℃, 400 ℃ and 700 ℃) were incorporated as active layers in the fabrication of chemoresistive sensing device detection of volatile organic compounds (VOCs). These layered showed enhanced chemical vapour sensing properties, especially for methanol and ethanol detection at room temperature. Therefore, although there are great limitations for applications of these CDs-derived layered allotropes in FTS reaction, these materials show a much better potential for applications in facile and cost effective VOC sensors. Further studies on this will be conducted.
Application of oxidative enzymes in membrane systems for the bioremediation of triazines in wastewater
(University of the Witwatersrand, Johannesburg, 2024-10) Lesaoana, Mahadi; Richards, Heidi L.; Brady, Dean
The prevalence of herbicidal pollutants present in various environmental matrices have become a global concern. The discharge and accumulation of s-triazine agrochemicals in effluents remains a major challenge, threatening the quality of freshwater resources. These are newly identified recalcitrant contaminants of concern (CECs) with complex structures, and inadvertent exposure poses deleterious ecological risks and human health-related adverse effects. Unfortunately, they have shown resistance to conventional treatment strategies, hence their persistence in wastewater treatment plant (WWTP) effluents and water bodies. Therefore, there is an urgent need for the exploration of alternative technologies for the effective eradication of such contaminants from water samples. The bioconversion of such micropollutants using oxidative enzymes like laccase is a promising research avenue, providing a sustainable, economically and ecologically benign strategy. The current research examined the potential of a hybrid biocatalytic membrane system to degrade common s-triazine agrochemical herbicides in aqueous solutions. Specifically, the use of Novoprime base 268 laccase coupled with hollow fibre polyethersulfone (PES) membranes was investigated for the bioremediation of atrazine (ATZ), ametryn (AMT), simazine (SMZ) , prometon (PMT) and terbuthylazine (TERB) in wastewater. In batch-mode reactions, major operating parameters (i.e. pH and temperature profiles, enzyme dosage and contact time) were varied for the laccase-assisted catalysis of s-triazine compounds. Optimised conditions provided highest removal efficiencies (> 88.9%) at pH 5.0, combined with a temperature of 25°C and 1.0 mg L-1 solution concentration after 24h reaction time. Through the addition of redox mediators viz. 2,2-azino-bis-3-ethylbenzothiazoline-6-sulphonic acid (ABTS), violuric acid (VA), vanillin (VA), syringaldehyde (SRA) and acetosyringone (ASR) recalcitrant triazine degradation was enhanced by 10 to 20 % at 1.50 mm. Subsequently, the performance of a standalone continuous flow-mode membrane system was evaluated firstly, using a bed adsorption column only operated under various conditions. The efficiencies were compared to batch-mode enzymatic experiments. The adsorption of triazines by PES was only weakly influenced by pH, and the optimum removal was attained at pH 5.0 (5.0 mg L-1), 2.35 g bed mass (14.0 cm height) and 24h column operation time. The overall removal percentages were 72.6%, 75.2%, 71.4%, 67.4%, and 68.2% for ATZ, AMT, SMZ, PMT and TERB, respectively. Although the results indicated satisfactory performances by both systems, their performance is limited when used as separate units (continuous membrane vs laccase reactor). A biocatalytic membrane system was achieved by integrating laccase into the dynamic packed-bed membrane column. Relevant process control design parameters of the fixed-bed biocatalytic column were carefully evaluated and recorded an optimum of 93.2 % removal efficiency as observed at a feed flow rate 2.0 mL min-1, at a bed height of 14.0 cm using an atrazine influent concentration of 5.0 mg L-1. Equilibrium dynamics of the breakthrough modelling were best fitted by Thomas model. Results attained demonstrated selectivity for triazines in matrix-matched real river water samples with remarkable recyclability after six successive operational cycles. This reflects the potential workability of the integrated system for extended enzymatic reactions evaluated under robust experimental conditions. As a benchmarking exercise, cost-analysis studies showed comparable projected scalability of our configuration at 1200 m3/d capacity at an estimated total cost of R7.036 mil.
Biophysical studies of metal chelate binding by HSA: Towards an understanding of metallodrug transport
(University of the Witwatersrand, Johannesburg, 2023) Sookai, Sheldon; Munro, Orde
Human serum albumin (HSA) is the most abundant blood protein, transporting many exogenous compounds including clinically deployed and investigational drugs that are generally organic in nature. HSA may largely influence the pharmacokinetics and pharmacodynamics of these drugs. Therefore, studying their interactions with HSA is vital in progressing drug development. In this thesis we present work on the synthesis and characterisation of five Schiff base bis(pyrrolide-imine) ligands that were metalated with either Au(III) (Chapters 2 and 3) or Pt(II) (Chapters 4 and 5). One of the ligands H2L1 was further metalated with Ni(II) and Pd(II) (Chapter 6). In Chapters 2 and 3 focus on a patented class of anti-cancer bis(pyrrolide-imine) Au(III) Schiff base chelates. Three Au(III) chelates were synthesized in Chapter 2 and underwent National Cancer Institute (NCI)-60 cytotoxic screening. Among them, AuL1 and AuL3 underwent full-five dose testing and recorded GI50 values of 7.3 µM and 11.5 µM, and IC50 values of 15.7 µM and 30.9 µM, respectively. AuL1 was tested further and found to be an interfacial poison of topoisomerase II at 0.5–5 µM and a catalytic inhibitor at 50 µM. In Chapter 3, two chiral tetradentate cyclohexane-1,2-diamine-bridged bis(pyrrole-imine) Au(III) complexes were reported, both of which were found to be cytotoxic in the NCI-60 screen. The chiral Au(III) chelates had a different mode of action compared to AuL1. Hierarchical cluster analysis suggest that their mode of action is similar to that of taxol. All five Au(III) chelates bound to HSA with moderate affinity (104–105 M–1) and minimally perturbed the structure of the protein. This highlights the potential for the Au(III) complexes to be transported by the HSA-mediated pathway. Chapters 4 and 5 focused on the synthesis of novel and previously reported Pt(II) Schiff base chelates to spectroscopically and computationally study their interaction with HSA and elucidate if the chelates could act as theranostic agents. It was found that switching the linking bis(imine) carbon linkage altered the binding affinity of the complex. However, the Pt(II) ion ensured that all three Pt(II) chelates preferred binding to Sudlow’s site II of HSA. The data was corroborated by molecular docking simulations and ONIOM calculations. Only 2 was found to be cytotoxic when irradiated with UV light but was found to act as a photosensitizer rather than a theranostic agent. Chapter 6 investigated the influence of d8 metal ions (Ni(II), Pd(II) and Pt(II) within the same ligand scaffold (H2PrPyrr) binding to HAS, which was investigated by steady state fluorescence quenching. The affinity constants, Ka, ranged from -3.5 -103 M−1 to-1- 106 M–1 at 37 C, following the order Pd(PrPyrr) > Pt(PrPyrr) > Ni(PrPyrr) >H2PrPyrr. The Pd(II) chelate was prone to hydrolysis and had a unique binding mode which we attribute to the unusually high binding affinity. The complexes uptake is enthalpically driven, hinging mainly on London dispersion forces. In summation, twelve metal complexes were successfully synthesized, of which 11 bound to HSA with a moderate binding affinity. The Au(III) chelates preferred Sudlow’s site I, while the Pt(II) chelates preferred Sudlow’s site II. Overall, the metal complexes bound fully intact to HSA.
Colloidal synthesis and characterization of molybdenum and tungsten-based phosphide electrocatalysts for hydrogen evolution reaction
(2022) Nkabinde, Siyabonga Sipho; Moloto , Nosipho
The production of hydrogen gas via hydrogen evolution reaction (HER) in acidic media has become an important area of research in light of the increasing demand for sustainable and environmentally friendly sources of energy. However, its large-scale production is currently being hindered by the lack of inexpensive and highly efficient non-noble electrocatalysts. Transition metal phosphides (TMPs) have transpired as favourable catalysts that can be prepared from cheap and readily available sources. Up to now, TMPs have been commonly prepared using solid-state and solid-gas reactions, which rely on the use of high temperatures and hence generate inhomogeneity in the prepared materials. Inhomogeneous materials are unattractive as catalysts because the correlation between a catalyst and its structural features cannot be systematically studied. For this reason, colloidal synthesis has emerged as a powerful method in the synthesis of TMPs as it allows for control over the resulting physical features (i.e. size, morphology, crystal phase, crystallinity etc.). The ability to tailor these physical properties provides room for improving the catalytic activity. By using the colloidal synthesis method, we have successfully prepared molybdenum and tungsten-based phosphide nanoparticles and studied the effect of their physical features on HER activity. In chapter 3, we report a facile colloidal synthesis method to produce an amorphous phase of molybdenum phosphide (MoP) by using trioctylphosphine (TOP) as a phosphorus source, molybdenum pentachloride (MoCl5) as a metal source and 1-octadecene (1-ODE) as a solvent/reducing agent. The use of the forementioned precursors promoted the formation of very small, shape controlled and well dispersed amorphous molybdenum phosphide (MoP) nanoparticles. Annealing (800 °C) of the amorphous MoP nanoparticles resulted in the formation of a crystalline MoP phase with a slightly bigger size but retained its dispersity and morphology upon exposure to high temperature. The amorphous and crystalline MoP phases were compared as HER electrocatalysts. HER results indicated that the amorphous MoP phase exhibited enhanced catalytic activity in hydrogen evolution reaction compared to the crystalline MoP phase. The high activity displayed by the amorphous MoP was attributed to the small sizes and the high density of unsaturated active sites characteristic of nanoparticles lacking long range crystalline order.
Design and synthesis of chronic wound healing collagen peptide mimics
(University of the Witwatersrand, Johannesburg, 2024) Lesotho, Ntlama Francis
The South African wound care management market is expecting a compound annual growth rate (CAGR) of 6.75%. The numbers are expected to further increase because South Africa has the highest number (4.6 million) of people living with diabetes in Africa. Annually approximately 2% of patients with diabetes develop diabetic foot ulcers and hence chronic wounds. Many chronic wound patients must deal with the financial burden, as many current wound treatment options are expensive, ineffective, and inconvenient. Intervention in the form of synthetic collagen mimetic peptides has been limited due to cytotoxicity and susceptibility to protease degradation. These challenges have, for an ardent time affected the clinical and commercial development of synthetic wound healing peptides. The aim of the current study is to develop novel wound healing peptides by derivatizing bioactive peptides into selective and protease stable peptidomimetics. All the synthesized peptides are meant to mimic the function of collagen type I. Thus, the designed peptides comprise of the retro- integrin binding type I collagen motif, -GFOGER-, the DGD tripeptide for attraction of growth factors, the retro- tripeptides Thr-Thr-Lys (TTK), Gly-His-Lys (GHK), Gln-Pro-Arg (QPR) and Glu-Glu-Met (EEM) to stimulate collagen production. The importance of collagen is evidenced by the fact that it features in all four stages of wound healing. This therefore means, its inclusion in any biomaterial meant to curb chronicity in wound healing is indispensable. With this approach, the biomaterial would overcome the challenge of excess matrix metalloproteinases (MMPs), which degrade both viable and nonviable collagen used in the wound healing process. It would further provide a collagen-based wound scaffold that compensates for the loss of collagen required for proper tissue regeneration. The applications of collagens in wound healing are immense. Due to its material properties, and apparent effectiveness, collagen has the potential to be utilized as an unprecedented treatment protocol for chronic, slow-healing wounds. Sixteen palmitate and adamantane collagen mimetic peptides were designed and successfully synthesized using the solid-phase peptide synthesis strategy. Eight of the sixteen peptidescomprise of lipophilic moieties (adamantane and palmitic acid) for improved membrane permeability and different collagen inducing retro-tripeptides namely, TTK, GHK, QPR and EEM (retro-DGD-GG-GFOGER-GG-TTK-Adamantane (NL010)/palmitate (NL009), retro-DGD- GG-GFOGER-GG-GHK-Adamantane/palmitate, retro-DGD-GG-GFOGER-GG-QPR- Adamantane/palmitate and retro-DGD-GG-GFOGER-GG-EEM-Adamantane/palmitate). Another eight are control peptides without the retro-tripeptides (retro-DGRGOF- Adamantane/palmitate, retro-GOP-GFOGER-GOP-Adamantane/palmitate, retro-GG- GFOGER-GG-Adamantane/palmitate and retro-DGD-GG-GFOGER-GG-Adamantane (NL008)/palmitate). The tertiary structure and secondary features (folding patterns) of the peptides were determined using the Nuclear Magnetic Resonance (NMR) and Circular Dichroism (CD). From NMR experiments, medium-range couplings were detected for NL010 and NL009, suggesting a possibility of alpha helices. Temperature 1H NMR experiment for the peptide DGRGOF- Adamantane proved the presence of cis and trans geometric isomers. CD experiments revealed that NL009 mainly has α-helix while NL010 mainly consists of a parallel conformation. Synthesis of adamantane and palmitate peptides with enhanced integrin binding was accomplished by incorporation of para-fluorophenylalanine in place of phenylalanine in the peptide retro-GG-GFOGER-GG-Adamantane/palmitate. The peptides were obtained in low yields but with increased hydrophobicity. Structural features for the improvement of the stability of the peptides against protease degradation were accomplished by the synthesis of peptoids and N-methylated peptides. The peptoids were synthesized in low yields but with increased hydrophobicity. The efficacy of NL009 and NL010 in wound healing was tested both in vitro and in vivo. In the former, the efficiency of both NL009 and NL010 in inducing migration of cells in a scratch wound was accentuated by hyaluronic acid. In in vivo studies, NL010 performed better than NL009. However, NL010 was outperformed by a comparator, Puramatrix® The peptides have the ability to induce migration of cells and therefore have an ability to create an environment needed for proper wound healing. The peptides could be used in place of native collagen and bring about proper healing of wounds
Development of eco-friendly building bricks derived from carbon nanotube-reinforced coal ash and low-density polyethylene waste materials
(University of the Witwatersrand, Johannesburg, 2024) Makgabutlane, Boitumelo; Maubane-Nkadimeng, M.S.; Coville, N.J.
This study reports on the incorporation of carbon nanotubes (CNTs) into the all-waste derived building bricks. The focus was on waste management and beneficiation of plastic waste and coal ash, which are generated in large volumes without sufficient recycling. The waste materials were characterized using a range of techniques to ascertain their properties for application. Multiwalled carbon nanotubes (MWCNTs) were synthesized using a facile floating chemical vapour deposition method (CVD) and their physicochemical properties were tested. Bricks with dimensions of 220 x 105 x 70mm were developed with an optimum 85:15 coal ash to plastic waste ratio respectively using a specialized reactor. The bricks were tested for compressive strength, split tensile strength, water absorption, strain, thermal stability and durability using oxygen permeability index, chloride conductivity index and water sorptivity index as indicators. Furthermore, environmental and financial sustainability and ecotoxicology were tested. At optimum conditions, high quality MWCNTs with a diameter of 83 nm, length of 414 μm and a carbon yield of 73% were obtained. The ID/IG ratio of 0.44, an oxidation temperature of 649 °C, a purity of 94% and surface area of 50.9 m2/g were achieved. Coal fly ash with a spherical shape, particle size of below 10 micron and a thermal stability of 680 °C was used as an aggregate for the bricks. The bricks (without CNTs) developed their maximum compressive strength of 11.9 MPa at 14 days. The incorporation of the CNTs improved the microstructure of the bricks by filling the voids and providing a bridging effect as reinforcement mechanisms. The optimum CNT loading of 0.05 wt.% produced bricks with a compressive strength of 22 MPa and tensile strength of 8.7 MPa, which exceeded the South African National Standards (SANS227:2007) requirements for building bricks by 450% and 625% respectively. The durability properties were improved as the CNT dosage was increased from 0-10 wt.%. The 0.05 wt.% bricks were categorized as “good” for all the durability indexes. The CNT containing bricks showed improved thermal stability and maintained their structural integrity. The chemical resistance also improved and the efflorescence was minimal on all the bricks. The utilization of waste in the bricks enabled resource conservation, reduced pollution and reduced cost compared to conventional bricks. When only considering the raw materials used, the cost of production per brick was $0.091. The ecotoxicology of the powdered brick samples was tested on Raphidocelis subcapitata (microalga) and Daphnia magna (aquatic organism) using leachates from neutral, acidic and basic mediums. Some heavy metals were leached above the threshold limit especially in acidic medium. The leachates were toxic to the test species at low concentrations and resulted in growth inhibition of the microalga and immobization of the aquatic organisms. The toxicity of the CNTs was inconclusive and dedicated tests are required to study their effect. With appropriate treatment of CFA, the waste derived CNT bricks have a great potential of being a sustainable alternative to the conventional bricks based on cost, properties and environmental impact
Dissolution of non-functionalized and functionalized nanomaterials in simulated biological and environmental fluids
(University of the Witwatersrand, Johannesburg, 2023-06) Mbanga, Odwa; Gulumian, Mary; Cukrowska, Ewa
The incorporation of nanoparticles in consumer products is exponentially high, however, research into their behaviour in biological and environmental surroundings is still very limited. In the present study, the static system and the continuous flow-through dissolution protocols were utilized to evaluate and elucidate the dissolution behaviour of gold, silver, and titanium dioxide nanoparticles. The behaviour of these particles was studied in a range of artificial physiological fluids and environmental media, to obtain a more precise comprehension of how they would react in the human body and the environment. The biodurability and persistence were estimated by calculating the dissolution kinetics of the nanoparticles in artificial physiological fluids and environmental media. The details of the current research are described as follows: An investigation into the dissolution of non-functionalized and functionalized gold nanoparticles was conducted as the first component of the research, examining the effect of surface functionalization on dissolution. The study determined the dissolution rates of functionalized and non-functionalized gold nanoparticles. Dissolution was observed to be significantly higher in acidic media than in alkaline media. The nanoparticle surface modification, particle aggregation, and chemical composition of the simulated fluid significantly affected the dissolution rate. It was concluded that gold nanoparticles are biodurable and have the potential to cause long-term health effect as well as high environmental persistency. This work has been published in the Journal of Nanoparticle Research and is presented in this thesis as Paper 1. Silver nanoparticles were also included in this study because they have many applications and industrial purposes. Therefore, their risk assessment was also of utmost importance. The results indicated that silver nanoparticle solubility was influenced by the alkalinity and acidity of artificial media. Low pH values and high ionic strength encouraged silver nanoparticle dissolution and accelerated the dissolution rate. The agglomeration state and reactivity of the particles changed upon exposure to simulated fluids, though their shape remained the same. The fast dissolution rates in most fluids indicated that the release of silver ions would cause short-term effects. This work has been published in Toxicology Reports and has been presented in this thesis as Paper 2. Although titanium dioxide nanoparticles are insoluble and undergo negligible dissolution, it was of utmost importance to investigate their behaviour in biological and environmental surroundings. This is as a result of the incorporation of these particles in everyday consumer products, in the nanosized range which raises concerns about their safety. Therefore, in Paper 3 presented in this thesis the dissolution kinetics of titanium dioxide nanoparticles in simulated body fluids representative of the lungs, stomach, blood plasma and media representing the aquatic ecosystem were investigated to anticipate how they behave in vivo. This work has been published in Toxicology In Vitro and presented in this thesis as Paper 3. The results indicated that titanium dioxide nanoparticles were very insoluble, and their dissolution was limited in all simulated fluids. Acidic media such as the synthetic stomach fluids were most successful in dissolving the particles, while alkaline media had lower dissolution. High ionic strength seawater also had a higher dissolution rate than freshwater. The dissolution rates of the particles were low, and their half-times were long. The results indicated that these particles could potentially cause health issues in the long term, as well as remain unchanged in the environment. This work has been published in Toxicology In Vitro and presented in this thesis as Paper 3. The last component of the research compared the dissolution kinetics of gold, silver and titanium dioxide nanoparticles through the use of the continuous flow-through system. The findings indicated that titanium dioxide nanoparticles were the most biodurable and persistent, followed by gold and silver nanoparticles. Therefore, it was suggested that product developers should use the OECD's guidelines for testing before releasing their product to the market to ensure its safety. This work has been published in Nanomaterials MDPI and presented in this thesis as Paper 4.
Electrocatalytic detection of biomarkers of tuberculosis and cervical cancer
(University of the Witwatersrand, Johannesburg, 2024-07) Peteni, Siwaphiwe; Ozoemena, Kenneth Ikechukwu
The need for simpler, low cost and efficient diagnostic methods remains a matter of urgency. This has opened numerous streams of research. Electrochemistry is a simple, cost effective and efficient method that has been used for the detection of several diseases such as tuberculosis (TB) and human papilloma virus (HPV). TB has been ranked amongst the most problematic diseases in HIV/AIDS burdened communities, this alone calls for concern. Biomarkers of TB not only indicate mycobacterium infection but can also assist in the early detection of TB which is highly beneficial for the infected person and the health care system. HPV is the causative agent for cervical cancer. Cervical cancer is ranked as the fourth disease that causes mortality amongst women. With that in mind, HPV-16 L1 early detecting means possible early detection of cervical cancer. In this thesis, methyl nicotinate (MN), which is one of TB’s biomarkers was detected in phosphate buffer solution (PBS, pH 6.0) and commercial human serum using cobalt nanoparticles supported on carbon derived from trimesic acid (TMA) (abbreviated as Co-NPs@CTMA) and biphenyldicarboxylic acid (BPDC) abbreviated as Co-NPs@CBPDC) as electrocatalysts. These electrocatalysts were obtained using microwave-assisted metal-organic framework process with TMA and BPDC as ligands. XRD data showed that these electrocatalysts are cobalt nanoparticles with dominant {111} and {200} phase with traces of cobalt oxide (CoO). XPS and Raman data showed that Co-NPs@CBPDC is defect-rich compared to the Co-NPs@CTMA counterpart. BET showed that CoPs@CBPDC has higher surface area and pore size and volume than the Co-NPs@CTMA catalyst. Both electrocatalysts showed reversible cobalt nanoparticle oxidation and reduction reactions, in the absence and in the presence of the MN, thereby allowing for a facile indirect electrochemical detection of this biomarker. The calibration curves showed low limit of detection (LoD) of 0.47 and 0.147 µM for Co-NPs@CTMA and Co-NPs@CBPDC, respectively. The higher performance of the latter is attributed to its enhanced physico-chemical properties compared to the former. Next, HPV-16 L1, which is the conventional high-risk antigen that is present in cervical cancer, was detected using onion-like carbon (OLC) and polyacrylonitrile fibre integrated with OLC (OLC-PAN) as electrode platforms. Two electrode platforms were used; onion-like carbon (OLC) and its polyacrylonitrile (OLC-PAN) composites. Both platforms led to the detection in a wide linear concentration range (1.95 fg/ml to 50 µg/ml), excellent sensitivity (>5.2 µA/log([HPV-16 L1, fg/mL]) and ultra-low detection of ca. 1.0 and 1.4 fg/ml for OLC-PAN and OLC-based immunosensors, respectively. The high specificity of detection was proven by experimenting with an anti-Ovalbumin antibody (anti-Ova) and native Ovalbumin protein (Ova). An immobilized antigenic HPV-16-L1 peptide showed insignificant interaction with anti-OVA in contrast with the excellent interaction with anti-HPV-16 LI antibody. The immunosensors showed satisfactory stability of ~ 3 days of re-usability. The application of the immunosensor as a potential point-of-care diagnostic (PoC) device was investigated with the screen printed carbon electrode which showed the ability to detect ultra-low (~ 0.7 fg/ml) and high (~ 12 µg/ml) concentrations. This study opens the door of opportunity for further investigation with other electrode platforms and realization of PoC diagnostic devicesfor screening and testing of HPV biomarker for cervical cancer.
Energy storage properties of carbon onion-carbon nanofibre composites containing transition metal compounds
(University of the Witwatersrand, Johannesburg, 2022) Khawula, Tobile Nokuphiwa Yollanda; Ozoemena, K. I.
The quest for electrical energy storage has been a key driver for researchers to come up with more effective means of storing this form of energy due to the intermittent nature of renewable energy sources. Several countries have swiftly adopted the transformative potential of renewables, in particular solar energy, while others have delayed the implementation due to complex policies surrounding renewable energy projects. A way forward would be innovative regulatory approaches that encourage the pairing of solar systems with other generation technologies, and with storage, to offer a “round the clock” supply. Rechargeable batteries and supercapacitors are widely employed energy storage systems. A rechargeable battery system offers high energy density, with lithium-ion batteries (LIBs) being the most widely used. For some applications, it is imperative that energy is delivered at a much faster rate. This characteristic feature is known as power density, and supercapacitors have proven to be much better than batteries in this case. The large-scale commercialization and adoption of a supercapacitor are hindered by its low energy density. The electrode material is a major determinant of the success of supercapacitors. Generally, these are supported on high surface area carbon materials. This study focused on the development of electrospun polyacrylonitrile (PAN) fibres embedded with onion- like carbon (OLC) and iron (II) phthalocyanine (FePc) particles, and encapsulation of the fibres with Molybdenum disulphide (MoS2). Furthermore, composite fibres were either integrated with manganese (III) oxide (Mn2O3) or engineered with defects for enhanced performance in symmetric supercapacitors. The synthesis of electrode materials was divided into four phases; In the first phase (1), OLC nanoparticles were embedded in electrospun PAN fibres and decorated with the Mn2O3 and evaluated as supercapacitor electrode materials. For enhanced interfacial electrochemistry and overall capacitance, the electrode material in (1) was encapsulated with MoS2 in phase (2). In phase (3) FePc embedded in the PAN electrospun fibres were evaluated for supercapacitor applications. Limited specific capacitance and poor cycling stability were observed, thus suggesting integrating OLC and further encapsulation with MoS2, in phase (4). The morphology of the fibres was vii engineered with defects in the form of Fe2+ vacancies to maximize the electrochemical reactions of the OLC/MoS2 fibre composite. The electrochemical properties of the fibre composite materials were investigated and OLC/Mn2O3-CNF exhibited a specific capacitance, energy and power density of electrodes were 200 F g-1, 44.63 Wh kg-1 and 3 235 W kg-1, respectively with excellent capacitance retention. While the MoS2 encapsulated and Mn2O3 decorated fibre composite, OLC/MoS2@Mn2O3 displayed a specific capacitance, energy and power density of 348 Fg-1 18.42 Wh kg-1 and 5 095 W kg-1, respectively. It is pertinent to note that the capacitance of the electrodes was retained throughout the 5 000 cycles of the charge-discharge test. Upon thermal treatment at 600 °C, FePc-PAN transformed into FeN4-CMF and exhibited a specific capacitance, energy and power density of 147 F g-1, 12.48 Wh kg-1 and 4 320 W kg-1, respectively. The vacancy-rich (FeN4)d-OLC- CNF@MoS2 composite obtained by the removal of Fe2+ atoms, showed a specific capacitance, energy density and power density of 481 F g-1, 76 Wh kg-1 5833 W kg-1, respectively. This study underscores strategic processes that can be adapted in the design, synthesis and optimization of supercapacitors-based electrodes for enhanced performance.
Fast oxide ion conductors for solid oxide fuel cells: average and local structure – property correlations in solid solutions of bi2o3
(University of the Witwatersrand, Johannesburg, 2023) Masina,Sikhumbuzo Mfanawemphi; Billing, David Gordon
In this thesis, substituted Bi2O3 systems were fabricated and characterized. W, Dy, Erand Nb were used as substituents in a goal to stabilise the highly conductive δ-Bi2O3like phases (hence forth referred to as the δ-phases) to ambient temperatures. Changes in both the average and local structures of the substituted Bi2O3 systems were correlated with the physical property conductivity. In the first part of the thesis, powder X-ray diffraction and Raman spectroscopy were used to show that WO3 on its own did not stabilise the δ-phase at ambient temperatures. The true equilibrium phase in the Bi2O3- WO3 system was a mixture of two tetragonal phases 7Bi2O3·2WO3 and 7Bi2O3·WO3. The co-doping strategy was used to fabricate the Bi2O3-Dy2O3-WO3 system (DWSB, where D =Dy, SB = stabilised Bi2O3). The δ-phase was stabilised with a minimum of 15 mol% total substituent concentration. Powder X-ray diffraction indicated that the δ- phases obtained in this system were metastable and degraded after isothermal annealing at ~ 500 °C for 100 hours. Addition of Er to the DWSB system to create the novel system Bi2O3-Dy2O3-Er2O3-WO3 (DEWSB, where E=Er) was found to significantly improve the stability of the δ-phase when annealed at virtually identical conditions as DWSB. The rest of the thesis is focused on the effect of each substituent cation on phase stability, local structure and the ageing phenomenon–the decrease in ionic conductivity upon isothermal annealing without any observable changes in average structure under powder X-ray diffraction. X-ray pair distribution function, X-ray absorption spectroscopy and photoluminescence were used to probe the local structure around the host Bi cations and some of the substituent cations (Dy, Er, W). The results indicated that some of the Bi cations are displaced away from the 4a site of the defect fluorite structure (Fm-3m) and that at the local level, the Bi cations assume an arrangement similar to that found in the monoclinic α-Bi2O3 phase. Dy and Er were also found to prefer local environments similar to those in their parent oxides. The resemblance increased as the material aged and might explain why the conductivity decreases upon ageing
Inclusion of nano-silver compounds in RO membranes as solutions to fouling by microbes and natural organic matter during seawater desalination
(University of the Witwatersrand, Johannesburg, 2023-08) Nchoe, Obakeng Boikanyo; Moloto, Nosipho; Sikhwivhilu, Keneiloe; Tetyana, Phumlani
The access to safe and potable water has become a salient discussion for governments across the globe. This is due to pronounced levels of the decline in volumes of available freshwater. Attributions to this phenomenon are mainly climate change, eutrophication, discharge of untreated effluent, heightened irrigation, and industrialization. Currently exploited freshwater sources are rivers, lakes, dams, glaciers, and aquifers. However, inconsistent rainfall patterns have rendered some of these sources as ‘stressed’, which is exacerbated by exponential population growth and misallocation of available freshwater. In hindsight, seawater was identified as a possible source of potable water. However, the high levels of salinity and miscellaneous contaminants (i.e., pathogens and natural organic matter) necessitates treatment of seawater prior its usage. Therefore, the purpose of this work is to develop rugged polyamide thin film nanocomposite (TFN) reverse osmosis (RO) membranes with antifouling properties for seawater desalination. TFN were fabricated by the inclusion of silver-based (i.e., silver sulfide) nanoparticles during interfacial polymerization of the polyamide active layer. Silver compounds are known to have superior antibacterial and photocatalytic properties, due to plasmonic and photo absorption properties. For this reason, silver oxide (Ag2O), silver sulfide (Ag2S), and silver chloride (AgCl) nanoparticles (NPs) were colloidally synthesized. These were then characterized and evaluated in photocatalytic and antibacterial applications. Cytotoxicity studies were also done to determine which of these NPs pose less risk to human health. The consolidation of data from these applications advised which of these NPs would be suitable for incorporation into the polyamide layer to produce fouling resistant TFN. Microscopic analysis depicted well-defined shapes, with average sizes of 23.0±5.7 (Ag2O), 30.6±7.4 (Ag2S), and 10.6±7.2 nm (AgCl). X-ray diffraction determined Ag2O, Ag2S, and AgCl NPs to have cubic, monoclinic, and cubic lattices, respectively. Optical spectroscopy determined Ag2O, Ag2S, and AgCl NPs to have band gap energies of 2.97, 3.11, and 3.05 eV, respectively. These observations inferred that crystalline NPs that exhibit surface plasmon resonance (SPR) in the visible region were successfully synthesized. SPR is a desired characteristic for photocatalysts, and indeed Ag2O, Ag2S, and AgCl NPs achieved humic acid degradation (HA) efficiencies of 86.2, 88.1, and 76.5%, respectively. In antibacterial studies, the broth micro-dilution method indicated that the minimum inhibitory concentration (MIC) values against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) for Ag2O, Ag2S and AgCl NPs were 0.03125, 0.125, and 0.125 mg/mL, respectively. The well-diffusion tests showed that Ag2O NPs had the largest zones of inhibition (ZOI), followed by Ag2S, then AgCl NPs. These observations demonstrated the concentration-dependent mitigation of bacterial cell proliferation. The NPs were further tested for cytotoxicity against human embryotic kidney 293 (HEK 293) cells. It was found that the cytotoxic concentration that rendered 50 % viability (CC50) were 0.0302, 0.3606 and 0.3419, and were obtained for Ag2O, Ag2S and AgCl NPs, respectively. This data implied that Ag2O NPs were the most toxic, while Ag2S and AgCl NPs were least toxic. In light of the above, Ag2S NPs were selected to be incorporated into TFN RO membranes. TFN RO membranes were fabricated by the addition of three different concentrations of Ag2S NPs in the aqueous phase to form the active polyamide (PA) layer on a polysulphone (PSF) support, namely 20, 30, and 50 mg. Fourier transform infrared (FTIR) spectroscopy detected vibrational peaks at 1659 cm-1 (amide I C=O stretch), 1542 cm-1 (amide II C-N stretch) 1481 cm-1 (C-H bend), 1385 cm-1 (C-O stretch), 1242 cm-1 (C-N stretch), and 779cm-1 (aromatic C-H and C=C wagging). The presence of aromatic and amide functional groups corroborated the formation of the TFN active layer, which is responsible for RO filtration of dissolved ions in water. Moreover, atomic force microscopy (AFM) revealed that average surface roughness decreased with increased Ag2S NP loading. TFN loaded with 20, 30, and 50 mg Ag2S NPs recorded water contact angles (WCA) of 54.1, 45.4, and 43.3°, respectively. The WCA of thin film composite membranes (TFC) without Ag2S NPs was recorded to be 73.5°. This demonstrated that the inclusion of Ag2S NPs increased surface hydrophilicity. In addition, salt rejection and water flux were higher for 30 mg loaded TFN (98 % and 32.7 L/m2h) compared to those of TFC (97% and 24.8 L/m2h). The bacterial growth inhibition was observed to be significantly high for 30 mg loaded TFN (80 %) compared to that of TFC (38 %). These observations indicate that the inclusion of Ag2S NPs significantly enhanced the performance of RO membranes and cost effectiveness of desalination.
Interfacial engineering of NbSe2 and TaSe2 to enhance their electrocatalytic activity for hydrogen production
(University of the Witwatersrand, Johannesburg, 2023-07) Kolokoto, Tshwarela; Moloto, Nosipho
There has been a need to replace fossil fuels, develop sustainable energy systems, and alleviate the negative environmental effects. These effects can be alleviated by developing efficient processes such as water-splitting, which can produce hydrogen gas in an environmentally friendly manner and, in turn, use it as a clean fuel. However, this process requires an effective electrocatalyst comparable to Pt and cost-effective. Herein, we demonstrate that the electrocatalytic activity of NbSe2 and TaSe2 can be improved by metal inclusion using interfacial engineering for the hydrogen evolution reaction (HER). The readily synthesised NbSe2 was decorated with 20% wt. Ni, 20% wt. Pt, 10% wt. Pt / 10% wt. Ni using two synthetic methods, namely the ex-situ and in-situ methods. The ex-situ samples had higher HER activities than the in-situ samples. Pt/PtO2-NbSe2 (derived from Pt decorated NbSe2 using the ex-situ method) showed a significantly enhanced HER activity compared to bare NbSe2. The Pt/PtO2-NbSe2 nanomaterial had the lowest overpotential, favourable kinetics and durability in an alkaline solution of 0.1 M KOH. The trend was as follows: Pt/PtO2-NbSe2 (Pt-decorated ex situ) > PtO-NbSe2 (Pt-decorated in-situ) > PtO/NiO-NbSe2 (Pt/Ni-decorated) > Ni/NiO-NbSe2 (Ni-decorated ex-situ) > Ni0.5Se/Ni(OH)2-NbSe2 (Ni-decorated in-situ) > NbSe2. In addition, NbSe2 was further decorated with 20% wt. Co using both the ex-situ and in-situ synthetic methods, and 10% wt. Pt / 10% wt. Co using the in-situ method. The ex-situ sample resulted in a higher HER activity compared to the in-situ samples. In particular, Co/Co3O4-NbSe2 nanomaterial (Co-decorated ex-situ) had the lowest overpotential, favourable kinetics and durability in an alkaline solution of 0.1 M KOH. The resultant trend was as follows: Co/Co3O4-NbSe2 (Co-decorated ex-situ) < Co3O4/CoSe2/PtO/PtO2-NbSe2 (Pt/Co-decorated in-situ) < Co3O4/CoSe2-NbSe2 (Co-decorated in-situ) < NbSe2. Consequently, the ex-situ method was the optimum synthetic method for forming NbSe2-based nanomaterials. TaSe2-based nanomaterials were formed similarly. TaSe2-based hybrids were formed by decorating TaSe2 with 20% wt. Ni, Co and Pt using the ex-situ method. The hybrid nanomaterials resulted in higher HER activities compared to pristine TaSe2 (i.e. Pt/PtO/PtO2-TaSe2 (Pt-decorated) > Ni/Ni(OH)2-TaSe2 (Ni-decorated) > Co/Co3O4-TaSe2 (Co-decorated) > TaSe2). Pt/PtO/PtO2-TaSe2 hybrid, in particular, resulted in the lowest overpotential under alkaline solutions (0.1 M KOH). Generally observed, was NbSe2-based electrocatalysts were better than TaSe2-based catalysts. In addition, the Pt-decorated ex-situ NbSe2 and Pt-decorated TaSe2 electrocatalysts were better than the model Pt/C catalyst, with the prior being the best overall. This is attributed to the basal sites of the NbSe2 and TaSe2. The ex-situ method was better than the in-situ method and this was due to the presence of metallic particles and the minimization of oxidation compared to the latter.
Microwave-assisted synthesis of palladium-based ferroalloy electrocatalysts for application in alkaline direct alcohol fuel cells
(University of the Witwatersrand, Johannesburg, 2024-11) Ramashala, Kanyane Nonhlanhla Eugenia; Billing, Caren; Modibedi, R. Mmalewane; Ozoemena, Kenneth Ikechukwu
This research work describes the study of Pd-based ferro-electrocatalysts for application towards direct ethanol fuel cells (DEFCs), direct ethylene glycol fuel cells (DEGFCs), direct glycerol fuel cells (DGFCs) and oxygen reduction reaction (ORR) operated in a basic environment. The initial part of the research was to explore the Pd-based monometallic and bimetallic (Pd/C and PdFe/C) by utilising varied methods such as the conventional sodium borohydride (NaBH4) and microwave-assisted technique (MW) towards the oxidation of glycerol (gly), intending to choose the best method viable for these catalysts. This study revealed that MW techniques tuned the physicochemical properties of Pd/C and PdFe/C by augmenting their crystallinity and defect. These led to improved electrocatalytic activities towards glycerol oxidation reaction (GOR) over NaBH4 technique. MW process as a powerful tool was further used in the entire study to synthesise bimetallic and trimetallic electrocatalysts in ethanol (EtOH), ethylene glycol (EG) and glycerol (Gly) oxidation reaction in an alkaline environment. The synthesised bimetallic catalysts studied in this research work were (PdFe/C, PdCo/C, and PdMn/C) at varied ratios of Pd: M (Pd2M/C (2:1) and PdM/C (1:1)). Amongst them all, Pd2Fe/C and PdFe/C were observed to be the most favourable catalysts towards all the alcohols, with the excellent specific activity of about, for EtOH (11.59 and 4.15 mA cm-2), EG (9.82 and 5.51 mA cm-2) and Gly (8.94 and 4.73 mA cm-2), respectively. The satisfactory performance exhibited by the PdFe/C electrocatalyst prompted the exploration of the second 3d transition metal (PdFeMn/C and PdFeCo/C), intending to investigate the synergistic behaviour between the non-noble metals and Pd. The XRD confirmed that these electrocatalysts are in a crystalline nature with a decrease in d spacing (from 0.2247 nm, PdFe/C to 0.2236 nm (PdFeMn/C)) after the insertion of Mn into PdFe/C. This was supported by the TEM images obtained for the PdFeMn/C catalyst with a particle size of sub 10 nm. The comparison studies towards EtOH, EG and Gly were investigated for all the electrocatalysts and there was a remarkable observation, which is dissimilar from the theoretical studies (DFT). Density Functional Theory (DFT) revealed that PdFeCo performed better in terms of Gibbs free energy, binding energy, and energy band gap than PdFeMn; however, the experimental studies favoring the performance of PdFeMn. The PdFeMn/C delivered the best electrochemical activities, including a superior electrochemical active surface area (ECSA), larger current densities and mass activity response, and less susceptibility to poisoning and high conductivity as compared to PdFe/C and PdFeCo/C electrocatalysts. Furthermore, the PdFeMn/C electrocatalyst exhibited remarkable electrochemical properties during the ORR (basic medium). Ultimately, the best two anode electrocatalysts (PdFe/C & PdFeMn/C) were explored and tested for the proof-of-concept in the two-electrode configuration with the micro-3D printed cell. The PdFeMn/C delivered improved µ-ethylene glycol fuel cell, µ-glycerol fuel cell, and µ-ethanol fuel cell activities with respective to high voltage and power density of 33.27 mW cm-2, 11.00 mW cm-2 and 45,80 mW cm-2 respectively, operated at 100 mV / s. These electrocatalysts have demonstrated promising results in advancing ADAFCs.
Preparation of nitrogen-doped multiwalled carbon nanotubes anchored 2D platinum dichalcogenides for application as hydrogen evolution reaction catalysts
(University of the Witwatersrand, Johannesburg, 2024-09) Mxakaza, Lineo Florence; Moloto, Nosipho; Tetana, Zikhona
The alkaline hydrogen evolution reaction (HER) (H2O + 2e − → H2 + 2OH−) is fast gaining traction as a sustainable hydrogen gas generation route but suffers from slow reaction kinetics because of the additional water dissociation step and large reaction overpotential. As such, the current state-of-the-art acidic medium Pt and Ru catalysts suffer from considerable loss of catalytic activity in an alkaline medium. We propose the development and use of platinum metal dichalcogenides for alkaline HER. Platinum dichalcogenides are 2D materials that offer the advantage of more exposed catalytic sites, show dramatic chalcogen-dependent electronic properties, and have a band gap (0.24 eV - 1.8 eV for PtS2 and PtSe2) thus extending the use of these materials to light-stimulated photo-electrochemical (PEC) HER. As such, PtS2 is reported to be a semiconductor, PtSe2 is semi-conductive/semi-metallic depending on the number of layers, and PtTe2 is metallic. The Pt-chalcogen covalent bond intensifies down the chalcogen group. Additionally, the interlayer interactions in Pt dichalcogenides are covalent, and just like the Pt-chalcogen bond, intensify as the chalcogen atom changes from sulphur to selenium to tellurium. This behaviour of Pt dichalcogenides results from the Pt bonding d orbitals and the chalcogen bonding p orbitals that are relatively close in energy than in other TMDs, and the difference in the energy becomes smaller and smaller down the chalcogen group. Herein, we report on the synthesis of PtSe2 and PtTe2 using the colloidal synthesis method for the first time and then applying them as electrocatalysts in alkaline HER. As mentioned, developing 2D materials results in band gap development, particularly in PtS2 and PtSe2. Following this, PtSe2 was explored as a photocathode in light-induced photo-electrochemical HER. Generally, semiconductors are poor electron transporters and one of the major requirements for an efficient PEC cathode is solar absorption, charge generation, and efficient charge separation. The charge separation properties of PtSe2 were improved by supporting this material on highly conductive, mechanically, and thermally stable nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs). In Chapter 3, we report on the effect of varying selenium precursors from elemental selenium, sodium selenite to selenourea on the colloidal synthesis of PtSe2 in a mixture of oleylamine and oleic acid at 320 ℃. All the reactions resulted in the formation of PtSe2 although PtSe2 prepared from selenourea is amorphous, evidenced by relatively broader XRD peaks and a smaller crystallite size. HER activity of the three PtSe2 catalysts was evaluated in 1 M KOH at a scan rate of 5 mV/s and PtSe2 prepared from selenium exhibited the earliest onset potential of 46 mV, overpotential of 162 mV, and a smaller Tafel slope of 112 mVdec-1. This material exhibits the smallest resistance to electron transport and a high electrochemical surface area. We then explored the effect of altering tellurium precursor from elemental tellurium to tellurium tetrachloride, and sodium tellurite. Unlike the PtSe2 synthesis, different platinum tellurite phases, PtTe2, PtTe, and the mixed phase PtTe: PtTe2 were produced from Te, PtCl4, and sodium tellurite, respectively. Of the three, PtTe2 exhibited the highest alkaline HER activity with an onset potential of 29 mV, an overpotential of 107 mV, and a Tafel slope of 79 mVdec-1. In the same chapter, we compared the catalytic activity of PtSe2 (prepared from Se) and PtTe2 (prepared from Te) catalysts. We determined that PtTe2 has a high surface roughness and electrochemical surface, leading to relatively higher activity than PtSe2. However, PtTe2 is metallic and therefore does not have a band gap, which implies that it cannot be employed in light-stimulated catalysis reactions. In Chapter 4, we explored the use of PtSe2 as a light-stimulated PEC alkaline HER catalyst. We used in situ colloidal synthesis to grow PtSe2 on the walls of N-MWCNTs to improve the overall electron transport properties of PtSe2. PtSe2 anchored on N-MWCNTs was also studied in the dark and under illumination using 1 sun (100 mW/cm2) to determine the influence of light on the HER catalytic activity of the hybrid materials. This study demonstrates that the light-stimulated HER activity of PtSe2 improves when minimal amounts of N-MWCNTs are incorporated in the PtSe2 sample matrix. This then leads to employing these materials as photocathodes in PEC HER.
Quantitative analysis of gold in low-grade tailings from different matrices, coupled with a study into the associated uncertainties
(University of the Witwatersrand, Johannesburg, 2023) Mashale, Kedibone Nicholine; Tshilongo, James; Chimuka, Luke
Gold is one of the precious group elements that is used for various purposes, such as jewellery, auto catalysts and as a form of investment. Various countries have gold reserves, with South Africa being the leading gold producer between 1980 and 2007. However, as of 2022, it is ranked as the eighth largest producer of gold, contributing 3% to the global contribution. The majority of gold is mainly mined from the Witwatersrand Basin in Johannesburg. It is well known that mining has been ongoing for decades, which means that a significant amount of land has been mined across the country. During gold mining, a large proportion of the ore material from which the gold is extracted is waste, together with the chemicals that were used, and this waste is termed mine tailings. This implies that based on the years that gold mining has occurred for and the depth of mining, a significant amount of the tailings have been deposited into free land around the mines, some of which are close to communities. The tailings consist of traces of gold that were left due to inefficient extraction processes and other components, such as base metals. The disadvantage of this is that due to the other chemical composition of these tailings, they have the potential to be dangerous to the environment. Some tailings contain minerals such as jarosite (KFe2(SO4)2(OH)6) that cause acid mine drainage, while heavy metals such as lead, mercury, arsenic and chromium can leach into surface and ground waters, causing pollution. Furthermore, they pose a danger if the dams that they are stored in collapse, which was recently witnessed in South Africa. Because of these factors, there have been various advances made towards the beneficiation of tailings, such as utilizing them to make glass or bricks for construction. A major advancement was the reprocessing of these mine tailings to recover or extract the remaining gold, which benefits both the environment and the mining houses. Therefore, in a move to support this initiative, scientists have taken to the laboratory to develop new or optimize existing methods for the extraction and quantification of gold, which is expected to be of a low grade over time. Various methods can be used for the quantification of gold, including the conventional fire assay, wet and dry chlorination and acid digestion. Most of these are suitable for medium- to high-grade gold ores but are known to experience challenges in regard to low-grade ores. The aim of this research was therefore to find the optimum method for the quantification of gold from mine tailings emanating from the Ventersdorp Contact Reef (VCR) and Barberton Greenstone Belt (GBS). Subsequent to chemical analysis, the samples were characterized for mineralogy using X-ray diffraction (XRD) and Brunauer‒Emmett‒Teller (BET) surface area
Structural Characterization of Bimetal-Phosphate Based Solid-State Electrolytes: A PXRD, PDF and XAS Study
(University of the Witwatersrand, Johannesburg, 2024) Nkala, Gugulethu Charmaine; Billing, David G.; Billing, Caren; Vila, Fernando D.; Forbes, Roy P.
In this work, NASICON-type lithium titanium phosphate (LiTi2(PO4)3, LTP) was synthesized following the conventional solid-state reaction methodology. Single and double-doped formulations of LTP were made, with the primary objective of improving the room-temperature ionic conductivity, for their application as potential solid-state electrolytes for all-solid-state Li ion batteries. The primary characterization technique applied was ambient-temperature powder X-ray diffraction (PXRD) at both laboratory and synchrotron experimental conditions. The Rietveld refinement approach was used to determine the qualitative and quantitative phase compositions of each sample, revealing the rhombohedral (R-3c, space group #167) main phase, with phosphate-based secondary phases. Total scattering data, through the pair distribution function (PDF) was applied, revealing lattice site preference during the substitution of Ti with Al, Sn and Dy at the 12c site. Further analysis through small-box modelling indicated the local structure deviation below 10 Å, from rhombohedral (R-3c) to monoclinic (P21/n, space group #14). The application of experimental X-ray absorption spectroscopy (XAS) revealed a stable 4+ oxidation state for Ti regardless of doping. However, the extended X-ray absorption fine structure (EXAFS) data showed that the replacement of Ti with Sn results in heavy disorder and subsequent changes in the PO4 tetrahedra, corroborating the findings from Raman spectroscopy. Theoretical XAS spectra were computed using FEFF, providing insights into the origins of experimentally observed XAS features from first-principles. Applying electrochemical impedance spectroscopy (EIS) to assess the ambient-temperature ionic conductivity, co-doped systems showed an improvement in the conductivity. The application of characterization techniques at various length scales has been demonstrated to provide insights into the mechanisms governing the performance of the solid-state electrolytes.
Studies on the chemistry and biochemistry of gold(III) carboxamide pincer chelates
(University of the Witwatersrand, Johannesburg, 2024-06) Razuwika, Rufaro; Nowakowska, Monika; Mathura, adhna
Cancer, a group of diseases characterised by the uncontrollable growth of abnormal or mutated cells within an organ, is a global concern. Metallodrugs have emerged as promising solutions to this pandemic, leading to intense research on different metal complexes. In this study, gold(III) carboxamide pincer complexes were evaluated as potential chemotherapeutic agents. The novel NNN-type carboxamide pincer molecules (ligands) effectively stabilising the gold(III) metal centre. The strong σ-donor properties of both the anionic and pyridine N groups further enhanced this stability. Ligands 1a-1f exhibited atropisomerism, a common feature in drug discovery, and containing special heterocycles such as quinolones, indazole, benzophenone, and phenanthroline, which are particularly relevant in drug development. Atropisomerism, however, was lost upon metalation of the ligands. Three complexes, 2d, 2e, and 2f, were successfully synthesised and isolated. Complex 2d was subjected to biochemical property testing and in vitro analysis due to its superior stability and solubility compared to 2e (poor stability) and 2f (poor solubility in the buffer solution used in the study). Speciation studies, combined with computational studies, suggested that 2d exists as a neutral complex under physiological conditions. This inert complex demonstrated stability against the reducing agent glutathione, indicating resilience to reduction under physiological conditions. DNA spectroscopic titration studies revealed that 2d exhibited intensive interaction with ct-DNA, with binding constants Ka1 = 1.48 x109 M-1 and Ka2 = 6.59 x105 M-1. This interaction resulted in a notable increase in the DNA melting point by 4 °C and an enhancement in viscosity in a dose-responsive manner. The DNA titrations, melting point, and viscosity studies suggested a dual binding mode of 2d to ct-DNA, involving base binding with a nearly equal preference for A, T, G, and C bases, and groove binding. Complex 2d exhibited a high affinity towards the transport protein HSA (Ka values were 1.57 x104 M-1), suggesting that it can be transported in the body by means of the HSA-mediated pathway, enhancing its efficacy and stability. In comparison to its affinity towards DNA, there is a significant difference allowing for the successful transfer of 2d from HSA to DNA. The poor solubility of complex 2d in aqueous environments may have hindered its cellular uptake, but binding to HSA could mitigate this, ensuring minimal interference with its cytotoxicity towards different cancer cell lines. MTT studies demonstrated that 2d has comparable cytotoxicity towards the breast cancer cell line MCF-7 with an IC50 of 9 µM. The IC50 for HT-29 was, however, too high to measure accurately (>100 µM). In conclusion, complex 2d exhibits promising anticancer properties based on its DNA binding studies and cytotoxicity evaluations. This suggests that this class of compounds can be applied in cancer treatments, with potential modifications to compounds 2e and 2f to improve their solubility and stability.
Synthesis and electrochemical properties of high-entropy spinel oxides, cobalt atomic clusters and zinc oxide as electrode materials for rechargeable zinc-air batteries
(University of the Witwatersrand, Johannesburg, 2024-07) Gaolatlhe, Lesego; Ozoemena, Kenneth Ikechukwu
This thesis investigated cathode and anode electrode materials for application in rechargeable zinc-air battery (RZAB). Two types of cathode materials were strategically studied in RZAB applications: (a) cobalt carbon composites of (i) cobalt atomic clusters (Co AC@CBPDC) and (ii) cobalt nanoparticles (Co NP@CBPDC), and (b) high-entropy spinel oxide (HESOx, containing five transition metals – Cu, Mn, Fe, Ni, and Co). The activities of these materials toward oxygen reduction reaction (ORR and oxygen evolution reaction (OER) were investigated in both half- and full-cell configurations as a proof-of-concept in RZAB cells in alkaline electrolyte. Considering that conventional zinc plate has several short-comings as an anode for RZAB, a new material, polydopamine-derived carbon-coated zinc oxide (ZnO@PDA-DC), was also synthesised and applied in RZAB as a possible alternative anode to the popular zinc plate. First, Co AC@CBPDC and Co NP@CBPDC were prepared using the metal-organic framework (MOF) route through the microwave-assisted solvothermal method and acid treatment. From the XRD results, the spectra showed dominant {111} and {200} phases, characteristic of metallic cobalt with a face-centred cubic (fcc). There were trace amounts of CoO observed indicating the coexistence of Co/CoO. From TEM imaging, Co AC@CBPDC was highly defective with a visible porous carbon structure than its counterpart (Co NP@CBPDC) and showed dispersed atomic clusters. BET data showed that Co AC@CBPDC had a higher surface area (144.8 m2/g) than the Co NP@CBPDC (33.25 m2/g). The improved physicochemical merits of the Co AC@CBPDC allowed for better ORR and OER activities than the Co NP@CBPDC in terms of low halfway potential (E1/2), onset potential (Eonset), overpotential at 10 mA/cm2 (ƞ10), potential gap (∆E) between the overpotential of OER and the halfway potential, and a higher kinetic current density (jk). The enhanced electrochemistry of the Co AC@CBPDC was attributed to the defects created by the acid treatment. As proof of real-life applicability, the Co AC@CBPDC electrocatalyst delivered an excellent air cathode in a parallel plate RZAB cell with notable OCV (1.23 V), peak power density (49.9 mW/cm2), a real energy density (477 mAh/cm2), long-term stability for 210 h, enhanced voltage retention, Coulombic efficiency (ca. 100 %) and DOD (51.3%), comparable to literature. In addition, an all-solid-state RZAB based on the Co AC@CBPDC catalyst gave a higher and constant OCV (1.73 V) at varied bending angles (0 – 180 degrees) and excellent stability. Second, new HESOx materials were prepared via the Pechini method at two different annealing temperatures of 500 and 750 oC (abbreviated herein as HESOx-500 and HESOx-750). P-XRD results showed that these are inverse spinel oxides, with {311} as the dominant phase. HR-TEM images proved that they are single nanocrystalline materials. XRD and BET data showed that the HESOx-500 is smaller in size, more porous, and has a higher surface area than its counterpart (HESOx-750). HESOx-500 showed superior ORR performance with an onset potential of 0.93 V and a E1/2 of 0.88 mV. The OER performance also showed improved ƞ10 compared to IrO2 with an overpotential of 340 mV at a current density of 10 mA/cm2, and a 45 ± 5.0 mV/dec Tafel slope, above the performance of IrO2 (66 ± 6.1 V/dec). The ∆E of HESOx-500 was 0.69 V. The material was further tested as a cathode material in a RZAB cell. The optimised RZAB cell showed remarkable performance with a theoretical potential of 1.67 V and long-term stability of 375 h at 10 mA/cm2. The performance was attributed to the high-entropy compositional design with a high number of surface oxygen vacancies and different metal oxidation states. Finally, having dealt with the issue of bifunctionality in RZAB, a new ZnO@C anode material was also considered. The ZnO@PDA-DC (where PDA-DC means polydopamine-derived carbon) was used due to its ability to form Zn2+ pathways. Electrochemical potentiodynamic polarisation tests were performed to understand and compare the corrosion inhibition effects in an alkaline medium (6 M KOH). The ZnO@PDA-DC showed better corrosion inhibition properties than the zinc plate and other samples: low corrosion current (icorr = 0.107 uA/cm2) and corrosion potential (Ecorr = 1.077 V), and a mixed inhibition effect, indicating reduced hydrogen evolution reaction and zinc dissolution. Due to the excellent corrosion inhibition properties of the ZnO@PDA-DC, it was then evaluated in the RZAB cell. The shallow galvanostatic charge-discharge cycle stability at 2 mA/cm2 was able to maintain 150 h in a RZAB at a voltage gap of 0.76 V to 0.80 V. The results demonstrated that enhanced rechargeability is possible with ZnO@PDA-DC for RZAB.
Synthesis of carbon nanodots-peptide conjugates decorated with germanium for bioimaging
(University of the Witwatersrand, Johannesburg, 2023-10) Machumele, Khanani Peggy; Makatini, Maya Mellisa; Maubane-Nkadimkeng, Manoko
The World Health Organization Global Cancer Observatory estimates that cancer caused 9.96 million deaths worldwide in 2020, making early detection crucial for diagnosis and treatment. Accurate identification of cancer plays a crucial role in the diagnosis and treatment process. It allows for customized and efficient therapies, minimizes unnecessary procedures and adverse effects, and improves the prognostic insights for patients and healthcare providers alike. The challenges in diagnosis include overdiagnosis, false positives/negative outcomes, and limited sensitivity. Advanced technologies are needed for better imaging accuracy and minimizing harm. This study aims to fabricate carbon dot-peptide conjugates to enhance bio-imaging capacity and selectivity. The peptides used are derived from the GKPILFF cell-penetrating peptide sequence and the RLRLRIGRR peptide, which is selective to cancerous cells. The Carbon dots were used to provide the photoluminescent properties required for bio-imaging of cancerous cells. Carbon dots (CDs) were synthesized using iso-ascorbic acid as the source of carbon using a microwave-assisted method. The nitrogen and germanium-modified carbon dots (Iso-N-Ge-CDs) demonstrated the highest photoluminescent properties compared to the unmodified CDs (Iso-CDs) and those with either N (Iso-N-CDs) or Ge (Iso-Ge-CDs). Photoluminescence emissions of longer wavelengths suitable for cell imaging were observed for the CDs, and the Iso-N-Ge-CDs demonstrated excitation-dependent emission wavelength behavior, pH sensitivity, and Fe3+ sensitivity. The 13 peptides derived from the peptide accelerating sequence GKPILFF and the cancer-selective peptide RLRLRIGRR were successfully synthesized. The peptides were characterized using Liquid Chromatography Mass Spectrometry (LCMS) and purified using preparative High-Pressure Liquid Chromatography (prep-HPLC). The secondary structure of the L-GKPILFF penetration acceleration peptide sequence (Pas) adopted a helical secondary structure. The D-GKPILFF derivative was found to adopt a random coil structure. These were confirmed using Nuclear Magnetic Resonance (NMR) techniques such as Total Correlation Spectroscopy (TOCSY) and Rotating Frame Overhauser Enhancement Spectroscopy (ROESY) NMR. The CDs-peptide conjugates were successfully synthesized, and the confirmation of conjugation involved multiple methods, including UV-Vis and PL techniques. To the best of our knowledge, the thesis incorporates the first study to demonstrate long-range interactions through ROESY NMR. The NMR analysis indicated that the helical structure of the peptide could be affected after conjugation, leading to notable peak shifts. Since the helical structure is crucial for the peptide's bioactivity and stability enhancement, NMR spectra with fewer structural changes in the peptide region may improve its biological properties. The research contained valuable information for scientists aiming to design and characterize Carbon dot-peptide conjugates with enhanced permeability and selectivity that can effectively deliver materials into cytosolic space.
Synthesis, characterization and investigation of the mode of action in the anticancer activity of novel platinum complexes
(University of the Witwatersrand, Johannesburg, 2024) Peega, Tebogo; Harmse, Leonie; Kotzé, Izak. A.
Cancer remains a global health concern, causing approximately 10 million deaths in 2020. Lung cancer, accounting for 18% of cancer-related deaths, and colorectal cancer, contributing 9.4%, are major contributors to this alarming statistic, emphasizing the urgent need for innovative and effective treatment options. Despite the success of platinum-based drugs such as cisplatin, carboplatin, and oxaliplatin, their limitations and severe adverse effects necessitate the exploration of alternative chemotherapeutic agents. This research project focused on synthesizing and characterizing square planar platinum(II) complexes bearing variations of two bidentate coordinating ligands; disubstituted acylthiourea and diimine ligands, each possessing unique physical and chemical properties. A series of cationic [Pt(diimine)(Ln-κO,S)]Cl complexes were successfully synthesized and characterized using nuclear magnetic resonance spectroscopy, infrared spectroscopy, mass spectrometry, and elemental analysis. The anticancer activity of these complexes was evaluated against two lung cancer cell lines, A549 and H1975, and a colorectal cancer cell line, HT-29. In vitro cytotoxicity studies included the determination of IC50 values of active complexes and assessing their cell death mechanisms through multiple biochemical marker assays. These included annexin-V binding, caspase-3/7 and caspase-8 activity, mitochondrial membrane potential (MMP), reactive oxygen species (ROS) and immunofluorescence for the expression of key proteins involved in the DNA damage response and oxidative stress response, such as p21 and haemoxygenase-1 (HO-1). A proteome array was employed to investigate the effects on apoptosis-associated proteins. The results indicated that these platinum complexes were more cytotoxic than cisplatin with IC50 values ranging between 0.68 μM and 2.28 μM. Further investigation showed that the platinum complexes induced cell stress, chromatin condensation, nuclear fragmentation, increased phosphatidylserine (PS) on the outer cell membranes and activated caspase-3/7. Platinum complexes induced intrinsic apoptosis in cancer cells, as evidenced by the loss of mitochondrial membrane potential and the absence of caspase-8 activity. Elevated ROS levels, increased HO-1 expression and increased expression of p21 suggested oxidative stress and DNA damage as the trigger source for intrinsic apoptotic cell death. The active complexes downregulated pro-survival proteins (IGFs) in lung cancer cells and anti-apoptotic proteins (survivin and HSP70) and upregulated pro-apoptotic proteins (p21, TRAIL R2), across the three cancer cell lines, indicating potential dual activation of apoptotic pathways. DNA binding studies indicated groove binding and intercalation as the mode of interaction with DNA. The findings highlight the potential of these platinum complexes as promising candidates for further development as cancer therapeutics.