Theses and Dissertations (Chemistry)

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    Fabrication of polymeric composite nanofiber materials and their antibacterial activity for effective wound healing
    (Vaal University of Technology, 2023) More, Dikeledi Selinah; Moloto, N., Prof.; Moloto, M. J., Prof.
    The synthesis of Ag and Cu nanoparticles was carried out using the thermal decomposition method in the presence of oleylamine as a capping agent. This method was used because it can produce uniform and monodisperse nanoparticles with controlled size distribution. The nanoparticles synthesized under various conditions were characterized by transmission electron microscopy (TEM), UV/Vis spectroscopy, photoluminescence spectroscopy (PL), and X-ray diffraction (XRD). The effect of precursor concentration on the morphology and size of the nanoparticles was investigated. It was observed that an increase in the precursor concentration resulted in an increase in particle sizes with different morphologies for both Ag and Cu nanoparticles. The increase in particle sizes for Ag nanoparticles was due to Ostwald ripening, while for Cu nanoparticles it was due to agglomeration, as Cu tends to oxidize in the atmosphere, leading to a change in particle size and shape. However, the ability to control and manipulate their physical and chemical properties depends on tuning their size and shape. Therefore, varying the precursor concentration helped in selecting the optimal concentration for this study. The nanoparticles produced were used in another study as fillers or additives for the production of nanofiber composites. The development of nanofibers by electrospinning process has led to potential applications in filtration, tissue engineering scaffolds, drug delivery, wound dressing and etc. The current study is an attempt to fabricate composite nanofibers that can be used as wound dressing material for effective wound healing. The approach involves the blending of two different polymers both being biocompatible and biodegradable were one is a natural polymer and the other is a synthetic polymer. In this study, different weight ratios of CS/PVA blends, Ag/Cu/CS/PVA, Ag/CS/PVA and Cu/CS/PVA composite fibers have been successfully prepared by the electrospinning process. The tip-to-collector distance was kept at 15 cm and the applied voltage was varied from 15 to 25 kV. The effects of the weight ratios applied voltage and the nanoparticles loading on the morphology and diameter of the fibers were investigated. The resultant fibers were characterized using scanning electron microscopy (SEM), XRD, Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric analysis (TGA) and UV-Vis spectroscopy. The SEM results showed that an increase the amount of chitosan in the CS/PVA blend resulted in a decrease in the fiber diameters while an increase in the voltage from 15 to 25 kV led to a decrease in the fiber diameters. Furthermore, an increase in fiber diameters was observed with irregular morphologies upon addition of Ag/Cu nanoparticles into the blend. The latter changes are perceived to be as a result of an increased conductivity and a higher charge density. The XRD results showed peaks which correspond to Ag in the face centred cubic. Ag peaks are more dominant than Cu peaks in the XRD of the mixed nanoparticles. The FTIR spectra of the Ag/Cu/CS/PVA composite fibers gave almost identical features as the blend. This proves that there was an interaction between CS and PVA polymer due to intermolecular hydrogen bonding. The TGA curves showed no significant effect on the thermal stability of the composite fibers upon addition of different nanoparticles loadings. The absorption spectra of the composite fibers showed an improved optical properties compared to the blend. For Ag and Cu nanoparticles composite fibers it was observed that addition of Ag nanoparticles in the blend resulted in an increase in fiber diameters with uniform morphology whereas for Cu resulted in a decrease in fiber diameters. Both Ag and Cu composite fibers showed an improved optical properties. The effect of CS/PVA, Ag/Cu, Ag, and Cu nanofibers on the selected microorganism (K.pneumoniae, S. aureus, P. aeruginosa, and E.coli) was evaluated using the disk diffusion method. It was observed that Ag/Cu/CS/PVA composite fibers showed greater activity against all microorganisms compared to Ag and Cu composite fibers. The alamar blue and Pierce Lactase dehydrogenase (LDH) assay were used to assess the effect of the blend and the composite fibers on cell viability and cytotoxicity, respectively. The results show that the prepared blend and the composite fibers did not have any toxic effect on human adipose derived stem cells (hADSC). The results also showed that as the concentration of Ag/Cu nanoparticles was increased the viability of the cells also increased after 24 hour incubation. More proliferation was observed in day 1 compared to day 3. The 30/70 blend showed more viable cell compared to the negative control. For Ag and Cu composite fibers the 30/70 CS/PVA blend increased cell proliferation after 3 days with 17% more viable cells compared to the negative control. These results show that the prepared blend with its composite fibers are biocompatible with human (ADSC) and may be suitable for use in biomedical application such as wound dressing.
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    Polymer intercalation of chemically bath deposited iron sulphide and nickel sulphide thin films
    (Vaal University of Technology, 2017) Molete, Puleng Alina; Moloto, M. J., Prof.
    In chemical bath deposition (CBD) method, deposition of metal chalcogenide semiconducting thin films occurs due to substrate maintained in contact with a dilute chemical bath containing metal and chalcogenide ions. Semiconducting nickel sulphide (NiS) and iron sulphide (FeS) thin films have been prepared on a glass substrate by varying the deposition parameters such as the concentration of solutions, deposition time, temperature and pH. Multi-layered thin films were deposited on glass substrate and the spin-cast conductive polymer, poly (3.4-ethylenedioxythiopene) polystyrene sulfonate (PEDOT: PSS) was intercalated. The characterization of the films was carried out using UV-Vis spectroscopy, scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM) and X-ray diffraction (XRD). Single layer nickel sulphide was deposited at room temperature, pH 10 and the deposition period of 3 hours, triethanolamine was used as the complexing agent. Iron sulphide was deposited for 6 hours at 70 °C with the pH of 2.5 using EDTA as a complexing agent. Generally the iron and nickel sulphide were prepared from their respective nickel or iron salt and the thiourea or thiosulfate as a source of sulphide ions in solution. SEM and AFM results show that the FeS film is evenly coated and has uniform grain size with the roughness of ~22.4 nm and thickness of ~23.8 nm. The optical absorption analysis of FeS showed the band gap energy of ~2.9 eV which blue shifted from the bulk. The EDX analysis confirms the compositions of iron and sulphur in FeS films. XRD pattern showed amorphous films for both FeS and NiS thin films due to the amorphous nature of the glass substrate. The optical data of NiS film were analysed and exhibited the band gap energy of ~3.5 eV and ~3.3 eV for successive ionic layer adsorption and reaction (SILAR), which is the modified CBD, both blue shifted from the bulk. The films were observed to have thickness value of ~35.7 nm and ~2.3 nm SILAR with the roughness of ~112.5 nm and ~35.4 nm SILAR from AFM results. SEM confirmed the uniformly distributed film presented by AFM analysis. The chemical composition of Ni and S were confirmed by EDX spectra. The PEDOT: PSS was intercalated between the FeS as the first layer and NiS as the top layer which gave the thickness of ~18.7 nm and roughness of ~115.2 nm from AFM analysis. PEDOT: PSS acted as a passive layer that protects and stabilize the FeS layer and NiS as the third active layer which enhanced the optical absorption of the film when using SILAR method for solar application.
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    Isolation of Pelargonium alchemilliodes L L'Her active compounds and their effects on bacterial growth and keratinocytes in vitro
    (Vaal University of Technology, 2019-07) Makanyane, Madikoloho Daniel; Ssemakalu, Cornelius Cano, Dr.; Okoli, Bamidele Joseph, Dr.; Mtunzi, Fanyana, Prof.
    Context: Pelargonium alchemilliodes L L' Her is an evergreen shrub, cultivated principally for the medicinal essence and decoction in Southern Africa for the treatment of skin problems, and wounds. Objective: the aim of the study was to optimize the extraction of phenolics and flavonoids from P. graveolens by response surface methodology with particular attention on the proliferative and cytotoxic effects on human keratinocytes, as well as the antioxidant and antibacterial activities and also to isolate active compounds. Materials and Methods: The optimization was achieved by Box-Behnken design. Extract, metabolite yields, and minimal inhibitory concentrations (MIC) were determined by gravimetric, spectrophotometric, and microdilution methods, respectively. The antiradical potentials were evaluated using the phosphomolybdate. 2,2-diphenyl-1-picrylhydrazyl, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), and lipid peroxidation assays, the diterpenoids were isolated and purified using open column chromatography, PTLC, and characterized with FTIR, NMR. The kinetics of the lipid protective activity was studied and fitted into models. The proliferative and cytotoxic effects were evaluated using the CellTiter® Blue cell viability and lactate dehydrogenase assay. Results: The regression coefficient r2 ≥ 0.9775 indicated a close correlation between actual and predicted values of the responses. The ideal parameter for the extraction of phenolics and flavonoids by macerations was determined as an extraction time: 9.63-12.01 h, material mass: 2.62-3.00 g, agitation speed: 143.11-197.11 rpm, and solvent volume: 68.06-69.87 mL. The optimal extractable acetone and methanol crude, flavonoids, and phenolic are (28.87±2.15%, 24.11±1.15%), (7.11±1.03 mg QE/g, 5.98±0.87 mg QE/g) and (58.08±0.88 mg GAE/g, 55.91±1.15 mg GAE/g), respectively. The detected different chemical groups of polyphenolic compounds such as alkaloids, saponins , sterols, terpenoids, flavonoids, tannins, phenols and cardiac glycosides from methanol and acetone extracts were in correlation with optimized yields. Two triterpenoids compounds 1-hydroxy-30-norlanosta-6, 8-diene and 1 2,3,4a,8,9,10,10a-octahydro-2-(2-hydroxypent-4-enyl)-4a-vinyl-1H-benzo[c]chromen-6(10bH)-one were isolated form methanol extracts. The main components of essential oils were citronellal (5.99%), citranellol (26.2%), geraniol (8.56%), citronellyl butyrate (20.3%), trans-farnesol (9.53%) and they were characterized by high amounts of oxygenated hydrocarbons (67.6%), followed by sesquterpene hydrocarbons and oxygenated sesquiterpene (9.32%) and the least being mornoterpene hydrocarbons (5.20%). Total antioxidant capacity and reducing power were comparable to standard gallic acid, while the antiradical activity has IC50 value of 0.18±0.03-8.98±0.15 mg/mL. Further, the lipid protective revealed a dose-dependent activity fitting into a pseudo-second-order kinetic model. MIC value of 1.56 mg/mL for extracts was registered against Staphylococcus aureus and salmonella typhi comparable to chloramphenicol. There was a significant (P < 0.05) increase in cell proliferation and viability when the extract was administered at concentrations of ≤50 μg/mL. However, at ≥100 μg/mL concentrations at ≤ 1000 μg/mL for essential oil exhibited a significnt cytotoxicity in comparison to the untreated cell. Conclusion: These biological activities are confirmation of the phytomedicinal application and possible source of pharmaceutical compounds. However, administration of the decoction should take into cognizance the antiproliferative effect at doses ≥100 μg/mL as well as the potential to induce and maintain keratinocyte proliferation at low concentration with an eye on the antiproliferative effect at concentrations ≥100 μg/mL, except the P. Alchemilliodes essential oils at ≤ 1000 μg/mL.
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    The effect of solar irradiated vibrio cholerae on the immunochemistry of dendritic cells
    (Vaal University of Technology, 2015-08-24) Ssemakalu, Cano Cornelius; Ubomba-Jaswa, Eunice, Dr.; Motaung, Keolebogile Shirley, Dr.; Mtunzi, Fanyana, Dr.; Pillay, Michael, Prof.
    Cholera is a waterborne disease caused by toxigenic strains of Vibrio cholerae. The spread of cholera in developing countries has largely been imputed to the unavailability of proper water treatment and sanitary infrastructure as well as poor hygiene. In order to prevent the contraction and spread of cholera the use of solar disinfection (SODIS) to treat water in waterborne endemic communities has been recommended by the World Health Organization (WHO). SODIS is a water sterilizing method that relies on natural sunlight to improve the microbiological quality of water. During SODIS the culturability of the water contaminating microorganisms is inactivated by the ultraviolet component of solar radiation. The success of SODIS treatment of water in alleviating the risks associated with the contraction of waterborne diseases such as cholera has been attributed to the effectiveness, with which the water is treated, simple application as well as low cost of materials required. Currently SODIS research has been dominated by studies geared towards understanding how the microbial inactivation occurs, enhancement of the disinfection process and health impact assessments. However, little to no research has been directed towards exploring the role played by the immune system following the consumption of the solar irradiated water pathogens such as V. cholerae. SODIS of microorganisms in water results in immunologically important microbial states and components that could induce an immune reaction or response. In view of the role of dendritic cells in shaping an immune response, the effect that solar irradiated V. cholerae in water has on the immunochemistry of the dendritic cells in vitro was investigated. Prior to the stimulation of the dendritic cells with the solar irradiated cultures of V. cholerae, the first objective required an evaluation on the impact that solar irradiation has on the production and secretion of the cholera toxin by V. cholerae in water. The results from this evaluation showed that solar ultraviolet radiation was incapable of inducing the secretion of the cholera toxin. Furthermore, there was extensive DNA degradation in the solar irradiated cultures of V. cholerae. The second objective was to investigate the ability for solar irradiated cultures of V. cholerae in water to induce the phenotypic maturation of immature dendritic cells in vitro. In order to achieve this objective, solar and non-solar irradiated, chemically/ heat inactivated and phosphate buffered saline (PBS) prepared cultures of V. cholerae as well as lipopolysaccharide (LPS) and cholera toxin-β (CTB) subunit were each used to stimulate immature dendritic cells. After 48 hours of stimulation the dendritic cells were assessed for the expression of CD54, CD80, CD83, CD86, MHC-I and MHC-II on their cell membrane. The results showed an increase in the expression of all the maturation phenotypic markers with CD54, CD86 and MHC-I being the most prominent ones on the surface of the dendritic cells stimulated with solar irradiated cultures of V. cholerae. The third objective was to assess the profile of the cytokines and chemokines secreted by the dendritic cells following their stimulation with solar and non-solar irradiated, chemically/heat inactivated and PBS prepared cultures of V. cholerae as well as LPS and CTB subunit. After 48 hours of dendritic cell stimulation the tissue culture media from each treatment was quantitatively and qualitatively analysed for the presence of interleukin (IL)-1α, IL-1β, IL-6, IL-7, IL-10, IL-12p40, IL-12p70, IL-15, IL-23, IL-27, macrophage inflammatory protein (MIP)-1α, MIP-1β, MIP-2, Regulated on Activation, Normal T cell Expressed and Secreted (RANTES) and tumor necrosis factor (TNF)-α. The analysis revealed that solar irradiated cultures of V. cholerae induced dendritic cells to secrete significant levels of pro-inflammatory cytokines in comparison to the unstimulated dendritic cells. Furthermore the profile of the cytokines and chemokines secreted by the dendritic cells in response to the solar irradiated cultures of V. cholerae in water was similar to that required to induce a T- helper (Th) Th2 immune response. The fourth objective was to assess the expression of the toll like receptor (tlr) genes by the dendritic cells following their stimulation with solar and non-solar irradiated, chemically/heat inactivated and PBS prepared cultures of V. cholerae as well as LPS and CTB subunit. After 48 hours of stimulation total RNA was extracted from the dendritic cells and subjected to real time quantitative polymerase chain reaction (RT qPCR) assay for tlr 1, 2, 3, 4, 5, 6, 9, 11, 12 and 13. The results showed no significant increase or decrease in the expression of most tlr genes in comparison to the unstimulated dendritic cells. This observation is synonyms with dendritic cell maturation. Taken together these findings show that solar irradiated cultures of V. cholerae were able to induce the maturation of immature dendritic cells in vitro. Furthermore dendritic cells stimulated with solar irradiated cultures of V. cholerae produced pro-inflammatory cytokines and chemokines. The results from this study suggests that the consumption of SODIS treated could provide immunological benefits.
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    Synthesis and characterization of electrocatalytic graphene for electrochemical sensing and bioelectronics
    (Vaal University of Technology, 2018-02) Osikoya, Adeniyi Olugbenga; Dikio, E. D., Prof.
    In this study, few layer graphene (Gr) and heteroatom graphene (HGr) were synthesized by chemical vapour deposition (CVD) method. Acetylene gas was used as carbon source for the synthesis of graphene, while a mixture of nitrobenzene and dichloromethane (ratio 1:1) were used as both carbon and dopant sources for the synthesis of the heteroatom graphene (HGr). A mixture of argon and nitrogen gases were carefully combined and used as carrier gasses and purge for both the synthesis of graphene and the synthesis of heteroatom graphene. X-ray diffraction (XRD) characterized showed that the as synthesized materials were crystalline materials, Raman spectroscopy indicated that the synthesized materials consist of sp2 hybridized carbon atoms, while scanning electron microscopy (SEM) and atomic force microscopy (AFM) results showed that the synthesized materials possess regions of 2 to 7 nm of thickness. Transmission electron microscopy (TEM) characterization also showed that the synthesized heteroatom graphene possesses about 5 to 7 layers with about 2 nm thickness, and x-ray photoelectron spectroscopy (XPS) result showed the presence of nitrogen, oxygen and chlorine in the lattice of the synthesized heteroatom graphene while the synthesized material still retained about 80% sp2 hybridization. The synthesized materials were used in the fabrication of modified bioelectrodes for electrobiocatalytic biosensing of glucose and hydroquinone. The fabricated bioelectrodes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CV characterization showed a diffusion-controlled electrode processes in al modified electrodes, while the EIS characterization showed the presence of both diffusion controlled and kinetic controlled impedance at the electrode-electrolyte interface. The fabricated GC/PEDOT-PSS/HGr/Lac modified bioelectrode exhibited a kinetic controlled impedance of 3150 Ω, while the fabricated GC/PEDOT-PSS/Gr/Lac modified bioelectrode exhibited a kinetic controlled impedance of 4138 Ω. Chronoamperometric experiments showed that the fabricated bioelectrodes exhibited swift electrobiocatalytic activity towards glucose and hydroquinone sensing respectively for graphene and heteroatom graphene. The graphene modified bioelectrode exhibited a linear response of 0.2 to 9.8 mM glucose concentration and a sensitivity of 87.0 μA/mM/cm2, while the heteroatom modified bioelectrode also exhibited a swift response to step by step addition of hydroquinone with a limit of detection of 2.07 μM and dynamic range of 2.07μM to 2.97 mM, thus indicating the tremendous potential of the materials in a wide range of electrobiocatalytic and bioelectronics applications.
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    Synthesis, fabrication and characterization of poly nanofibers and investigation of their adsorption properties
    (Vaal University of Technology, 2017-06) Shooto, Ntaote David; Skhwivhilu, L., Dr.; Wankasi, D., Prof.; Dikio, E. D., Prof.
    A major challenge for this generation is cleaning up heavy metal pollution disposed during industrial, domestic and agricultural activities. So, to obtain clean water resources, new treatment technologies are needed that can be applied to a broad range of highly toxic heavy metals in water. In this study, metal organic frameworks (MOFs) were synthesized from 1,2,4,5-tertabenzene carboxylic acid with metal salts of; cobalt, copper, iron, antimony, strontium and lanthanum through solvothermal method. The synthesized MOFs were reacted with polyvinyl alcohol (PVA) by electrospinning. To the best of our knowledge it is for the first time that such hybrid materials are synthesized and reported. PVA/MOF materials were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry analyzer (TGA). The SEM micrographs of PVA/MOFs materials showed relatively uniform nanofibers that were non-beaded and entangled. Some formed patches, while others were partially cross linked. TGA analysis revealed that PVA/MOF nanofibers exhibited higher decomposition temperature than PVA nanofibres. Thus, it confirmed the interactive force between MOF and PVA nanofibres. FTIR plots also exhibited shifts in critical functional group positions, thus it confirmed that there was a given amount of MOFs embedded in the electrospun fibrous mat. PVA/MOFs materials were used in the adsorption of lead ions in solution to study the effects of temperature, time dependant studies and concentrations. The batch adsorption experiments were performed at five different Pb(II) ion concentrations (20, 40, 60, 80 and 100 mg/L), four different temperatures (25, 40, 60 and 80 oC), time dependent studies ranged from (5, 10, 30 and 60 min) and pH of all Pb(II) solutions were recorded to be 5.05. The results indicated that the uptake performance of PVA and PVA/MOFs nanofibers significantly changed with concentration, temperature and time. The PVA/MOFs nanofiber hybrids demonstrated greater adsorption percentage and adsorption capacity for Pb(II) ions than PVA nanofibers. PVA nanofibers showed moderate adsorption percentage and capacity performance of 25.5 % and 44.13 mg/g (meaning 44.13 mg of Pb(II) per gram of PVA nanofibers) while PVA/MOFs nanofibers showed improved percentage and capacity perfomance (PVA/Cu-MOFs 76.36 % and 152.72 mg/g), (PVA/Co-MOFs 59.41 % and 99.28 mg/g), (PVA/La-MOFs 92.27 % and 184.03 mg/g), (PVA/Cd-MOFs 83.19 % and 165.94 mg/g), (PVA/Sb-MOFs 50.66 % - 91.57 mg/g), (PVA/Sr-MOFs 58.85 % - 124.82 mg/g) and (PVA/Fe-MOFs 56.76 % - 108.82 mg/g). The adsorption data of Pb(II) ions on PVA and all PVA/MOFs nanofibers showed that a pseudo-second order kinetic model was more suitable than a pseudo first order kinetic model. The adsorption rate was much faster on PVA/MOFs nanofibers. This is marked by lower activation energy compared to PVA nanofibers activation energy. The Temkin model did not correlate well with all the adsorption data. On the contrary, Freundlich and Langmuir isotherm models described the adsorption data adequately. All PVA/MOFs nanofibers followed Langmuir isotherm model, only PVA nanofibers followed Freundlich isotherm model. The PVA and PVA/MOFs nanofibers gave negative values of enthalpy change (ΔHo) and negative values of Gibbs free energy change (ΔGo) showing the adsorption processes were exothermic and spontaneous. Moreover, obtained positive entropy changes (ΔSo) on PVA, PVA/Fe-MOF, PVA/Cu-MOF, PVA/Co-MOF and PVA/Sb-MOF nanofibers showed that the sorped Pb(II) ions were not restricted on the electrospun nanofibres and physisorption mechanism was dominant, while negative entropy changes (ΔSo) on PVA/Sr-MOF and PVA/La-MOF nanofibers indicated that chemisorption was more dominant. The influence of ubiquitous cations such as Ca(II) and Mg(II) on the adsorption of Pb(II) ions onto PVA and PVA/MOF nanofibers was also assessed. The results showed that the ubiquitous ions had no significant influence on the sorption of Pb(II) ions. Current investigation provides a method to develop novel PVA/MOFs nanofibers hybrid adsorbents for water purification system. The adsorption capacities and removal achieved with the PVA/MOFs nanofibers sorbent were higher than those for PVA sorbent. The electro spun nanofiber sorbents presents an efficient alternative for pre-treating lead ions in aqueous solutions. Results from this research demonstrated that higher performance novel nanofibers, which possessed higher adsorption percentages and capacity capabilities were obtsained far exceeding some of the commonly used adsorbents, were obtained.
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    Synthesis and characterization of metal oxide thin films, metal sulfide and metal oxide polymer nanocomposites and studies of their application in water treatment
    (Vaal University of Technology, 2017-08-10) Xaba, Thokozani; Moloto, N., Prof.; Moloto, M. J., Prof.
    The study based on thiourea derivatives has received significant interest from several disciplines due to their variable bonding modes, promising biological implications and their complexation capacity. Thiosemicarbazones are a stimulating type of ligands that reveals a diverse range of biological activities. They are effectual intermediates for the production of pharmaceutical and bioactive materials which makes them very useful in the field of medicinal chemistry. The FTIR spectral variations in the stretching frequencies of C=N, C–N and C=S that appeared at 1663, 1327 and 726 cm-1, respectively confirmed the formation of the ligand. The present study describes the preparation of (Z)-2-(pyrrolidin-2-ylidene)thiourea ligand for the synthesis of ZnS, CdS and Ag2S nanoparticles via homogeneous/chemical precipitation technique. The effect of different capping agents such as starch, PVP, PEG, PVA, and the role of ammonium hydroxide solution during the synthetic processes was investigated and distinguished. The study based on the effect of capping molecule on the formation of nanoparticles proved that the capping agent has a great influence on the formation of nanoparticles. The FTIR spectra of the capped nanoparticles revealed the shift toward the higher frequencies compared with the uncapped metal sulfide nanoparticles. The metal sulfide nanoparticles also showed an increased in energy band gaps which were different from the bulk materials. The 2-hydroxy-1-naphthaldehyde is regarded as a low-cost ligand which has also been widely used in biological synthesis to determine free amino acid groups. The metal complexes of this ligand are easily prepared and can be used to synthesize metal oxide nanomaterials at low cost which are environmentally friendly that can be expended in bio-applications. The preparation of the Zn, Cd and Ag complexes based on the bis(2- hydroxy-1-naphthaldehydate ligand through the reaction desired metal acetate are reported and confirmed by FTIR spectroscopy, elemental analysis and thermogravimetric analysis (TGA). There has been a great research significance for the synthesis of metal oxide since such materials have high specific surface area and a high fraction of surface atoms. The synthesis of ZnO, CdO and Ag2O nanoparticles through thermal decomposition of the Zn(II), Cd(II) and Ag(I) complexes into trioctylphosphene oxide (TOPO) and/or hexadecylamine (HDA) at different decomposition temperatures is reported. The study proved that the combination of oleylamine as a solvent and TOPO as a capping molecule produced controlled shaped and reasonably dispersed particles. The XRD patterns of all the metal oxide nanoparticles synthesized with TOPO were showing face-centred cubic structures. These metal oxide based complexes were also used as single source precursors to prepare metal oxide thin films at different annealing temperatures on the glass substrate using different methods such as annealing, thermal decomposition, aerosol assisted chemical vapour deposition (AACVD) methods. The optical absorption and size distribution of the synthesized nanoparticles and thin films have been explored using XRD, SEM, AFM, FTIR, PL and UV-Vis spectroscopy techniques. The results show that the decomposition temperature has a huge effect on the formation of the nanomaterials. The SEM images of the as synthesized nanoparticles revealed different shapes of the particles as the decomposition temperature is increased. A change in X-ray diffraction parttern was observed when the decomposition temperatures were increased. The capped metal sulphides and metal oxide nanoparticles were then allowed to react with polydadmac or chitosan to form the polymer nanocomposites. The optical absorption, luminescence properties, size distribution and the bonds distribution of the polymer nanocomposites were characterized with UV-Vis, PL and FTIR spectroscopy. The structural and morphological properties have been studied by XRD, TEM and SEM. The absorption analysis of the prepared nanocomposites revealed the properties of both nanoparticles and polymers. Chitosan and polydadmac are biopolymers that have been proven as the best adsorbents to remove the heavy metal ions from wastewater.In this study, polydadmac and chitosan based metal sulphide and metal oxide nanocopmposites were used as adsorbents for the removal of Fe(III) from the wastewater. The batch experiments were conducted to achieve the optimum conditions. The effect of pH, contact time, and initial metal ion concentration were also determined. The pH = 8 was found to be the optimum pH for the removal of Fe(II) ions from the water sample by utilizing pure chitosan and chitosan nanocomposites as adsorbents.
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    Comparative study of the immunomodulatory effect of solar and photonically inactivated salmonella enteritidis on dendritic cells in-vitro
    (Vaal University of Technology, 2022) Adeniran, Dorcas Oluwaseun Taiwo; King, Abia Akebe Luther, Dr.; Ssemakalu, Cornelius Cano, Dr.
    Salmonellosis is a food and water-borne disease that affects humans, especially those that are immunocompromised as well as children and the elderly. This disease is caused by a variety of Salmonella species. Salmonella Enteritidis (SE) is the most frequently isolated serovar in infections occurring in humans and from animals all over the world. Salmonella Enteritidis is found in many animals and can survive in environmental samples for several weeks under ideal conditions. The failure of waste water treatment plants, agricultural pollution, and storm water runoff into natural water sources has led to an increase in the presence of Salmonella in water. The possibility of fecal contamination of water remains high in resource poor communities where sanitary and hygienic practices are inefficient or insufficient. However, many resource poor communities are using solar disinfection (SODIS) as a means of treating water prior to consumption. The SODIS method is achieved by exposing bacterial contaminated water to the sun for the period of 6 to 8 hours. The reliability of the SODIS process depends on factors such as temperature, dissolved oxygen and most importantly UV-A radiation. These factors cannot be controlled in a natural environment due to fluctuations or climatic changes in weather conditions. Instead of relying only on SODIS, other methods such as the use of a photonic device to disinfect microbiologically water are being used. The main aim of this study is to compare the immunomodulatory effect of solar irradiated and photonically inactivated S. Enteritidis on dendritic cells in-vitro and to provide supporting information on the immunological benefits on the consumers of SODIS drinking water through a SODIS mimicking device. To achieve this aim, there was a need to optimize the SODIS and photonic inactivation conditions of S. Enteritidis. Salmonella Enteritidis cultures were exposed to solar irradiation during spring, summer and winter as well as photonically using an ultraviolet light. The result revealed that the inactivation efficiency of Solar ultraviolet radiation (SUVR) on S. Enteritidis was season dependent. A total loss of activity was observed in S. Enteritidis during summer and no regrowth was observed. With the photonic device, a combination of UV and oxygen inactivated the S. Enteritidis to below detectable limits. This study compared the protein profiles of solar irradiated and photonically inactivated S. Enteritidis using SDS-PAGE. The results showed a gradual decrease in the concentration of the protein banding patterns with time in S. Enteritidis that was either solar irradiated or photonically inactivated. The ability of the solar and photonically inactivated S. Enteritidis to induce maturation of dendritic cells in-vitro was also investigated. There was a significant increase in CD80 when the 8-hour solar inactivated samples of S. Enteritidis was used to stimulate the dendritic cells. The higher levels of co-stimulatory molecules observed suggested the possible involvement of these molecules in antigen uptake and presentation to produce a specific immune response. This finding will contribute towards the understanding of the immunological effects that may be generated from consuming SODIS water and whether it may result in an immune reaction or response. Although the current study shows that solar irradiated and photonically inactivated cultures of S. Enteritidis were able to induce the expression of key immunological surface makers by dendritic cells, further studies are required to corroborate the findings of this study.
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    Adsorption of nitrate and fluoride anions from aqueous solutions using doped magnetite-pinecone nanocomposites
    (Vaal University of Technology, 2022-03-23) Frans, Nonhlanhla; Ofomaja, A. E., Prof.; Akpotu, S., Dr.; Pholosi, A., Prof.
    The increasing rate of pollutants, such as nitrate and fluoride from industrial and agricultural sources in the environment, especially in water bodies, is becoming alarming. Excessive nitrate and fluoride concentration in water cause environmental toxicity and hazard such as eutrophication and toxic, chronic illnesses such as methemoglobinemia. Hence, there is an urgent need to remove these pollutants from water. There have been a few successful strategies for the purification of pollutants contaminated water. Adsorption has been applied to remove pollutants from aqueous media due to its flexibility, ease of use, cost-effectiveness and ability to adsorb contaminants at low concentrations. Various adsorbents have been applied to remove nitrate and fluoride anions, and doped magnetic has shown to be effective in removing these anions. In this study, manganese doped magnetite coated pinecone (Mn-MNP-PCP) and lanthanum doped magnetite coated pinecone (La-MNP-PCP) nanocomposite were prepared using the co-precipitation method. Fourier Transform Infra-Red (FT-IR), Scanning electron microscopy (SEM), Energy-dispersive x-ray spectroscopy (EDS), Thermo-gravimetric analysis (TGA), X-ray diffraction (XRD) were used to determine the surface groups, structure and morphology, chemical composition, thermal stability and phase determination (amorphous or crystalline) structure of the synthesised Mn-MNP-PCP and La-MNP-PCP adsorbents, respectively. In addition, batch adsorption experiments were conducted to evaluate the effects of solution pH, adsorbent dose, initial solution concentrations, contact time, adsorption kinetics, adsorption isotherm and the impact of co-existing anions on the adsorption of nitrate and fluoride ions. The mechanism of adsorption processes was also determined using equilibrium isotherm modelling results and thermodynamic parameters. The maximum adsorption capacity of Mn-MNP-PCP and La-MNP-PCP adsorbents for nitrate adsorption was 22.8 mg/g and 37.7 mg/g at solution pH 4, while the adsorption efficiency was 45.6% and 75.4%. Fluoride removal occurred at pH 2 with the adsorption capacity of 46.2 mg/g and 44.77 mg/g with the removal efficiency of 92.4 % and 89.6% on both Mn-MNP-PCP and La-MNP-PCP adsorbents. The optimum adsorbent dose for both Mn-MNP-PCP and La-MNP-PCP in the adsorption of nitrate and fluoride was 1 g/L. The optimum time for the uptake of nitrate and fluoride onto MNP-PCP and La-MNP-PCP was between 15 – 20 min. The competing phosphate and sulphate ions impacted the nitrate adsorption, while the presence of carbonate and chloride had positive nitrate adsorption onto both Mn-MNP-PCP and La-MNP-PCP nanocomposites. The decrease in nitrate adsorption may be attributed to the lower affinity of Mn-MNP-PCP and La-MNP-PCP for nitrate and a competition between the nitrate ions and co-existing anions for the active sites. The presence of all competitive ions decreased the fluoride adsorption onto Mn-MNP-PCP and La-MNP-PCP nanocomposites. The multi-valent anion with higher charge density have been reported to be more readily adsorbed than monovalent anion. The equilibrium data for nitrate and fluoride ions uptake was best described by Langmuir isotherm, which predicts the formation of ionic or covalent chemical bonds between the adsorbent and adsorbate. In the same vein, pseudo-second-order model is considerably suitable for nitrate and fluoride ions adsorption, which showed that their uptake was fast. Conclusively, La-MNP-PCP adsorbent is an effective adsorbent for nitrate adsorption, while Mn-MNP-PCP effectively trmoved fluoride ions from the aqueous solution.
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    The fabrication of ClNCNTs/Fe3O4 nanoparticles for the removal of Pb2+ ions in aqueous solution
    (Vaal University of Technology, 2021-12-13) Sebake, Morongwa Sowela Mary-Jane; Maubane-Nkadimeng, Manoko S., Dr.; Maboya, Winny K., Dr.
    Removal of wastewater pollutants is urgent as they are continuously defiling the limited freshwater resources, affecting the ecosystem, aquatic and terrestrial life. Carbon nanotubes-based adsorbent materials are effective for removal of wastewater pollutants owing to their large specific surface area. Surface modification of carbon nanotubes (CNTs) can mediate specific pollutant adsorption and increase CNTs colloidal stability and chemical reactivity. Heavy metal pollution of wastewater is one of the major threats, as this metals can be toxic to humans when present at certain concentrations in drinking water. This study report the synthesis of chlorine functionalized and nitrogen doped carbon nanotubes (ClNCNTs) loaded with iron oxide nanoparticles and their use as adsorbents for Pb2+ ions in aqueous solutions. Carbon nanomaterials that are functionalized with chlorine and doped with nitrogen were successfully synthesized. This was done through pyrolysis of a mixture of dichlorobenzene and acetonitrile (in a 1:1 volume ratio) over 10% Fe-Co/CaCO3 bi-metallic catalyst via chemical vapour deposition (CVD) method. Addition of chlorine and nitrogen to the CNTs was to enable defect and disorder creation on the surface of the nanotubes which is envisaged to create nucleation sites on the their surface for better adhesion of the iron oxide nanoparticles. Different loadings of magnetite (Fe3O4) nanoparticles on the surface of the ClNCNTs was achieved using a co-precipitation method. The synthesized materials were charaterized by Raman spectroscopy, Transmission electron microscopy (TEM), Powder X-ray diffraction (PXRD) spectroscopy, Thermal gravimetric analysis (TGA), Brunauer Emmett and Teller (BET) and X-ray photoelectron spectroscopy (XPS). Highly defected CNTs, some with hollow and others with bamboo-compartments due to nitrogen inclusion were obtained. The effect of metal salt concentration in wt.% (10, 20, 30 and 53 wt.%) was investigated. The increase in wt.% loading has resulted in an increase in surface area, and a decrease in thermal stability as a result of defected Fe3O4/ClNCNTs. In addition, agglomeration was observed at 30 and 53 wt.% loading, due to large amount of iron present. The identity of the Fe3O4 nanoparticles was confirmed by PXRD and XPS with two iron peaks deconvoluted at 725.6 eV and 721 eV respectively. The percentage loading of the Fe3O4 nanoparticles at the surface of the ClNCNTs was affirmed by TGA analysis, where the residual mass obtained from TGA were closely related to the mass percentages added. Different nitrogen environments namely, the quatenary, pyridinic, pyrollic and nitrogen oxides were also observed, whilst chlorine could not be deconvoluted because it was present in very limited amount probably it was masked by the iron oxide nanoparticle. Thus, a 20 wt.% Fe3O4/ClNCNTs was chosen as an optimum, due to uniform distribution of spherical nanopaticles observed along the radial length of ClNCNTs that had an average size of 10 ± 4.5 nm. The synthesized ClNCNTs and a nanocomposite made from a 20 wt.% Fe3O4/ClNCNTs were applied in the removal of Pb2+ ions from aqueous solution. The results obtained showed that a nanocomposite made from a 20 wt.% Fe3O4/ClNCNTs had a better adsorption capacity of 17.0 mg/g as compared with 14.8 mg/g for ClNCNTs.
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    Copper oxide-carbon catalysts for the oxidation of methylene blue
    (Vaal University of Technology, 2020) Makamu, Anza Reliance; Ofomaja, Prof.; Viljoen, E. L., Dr.
    Organic water pollutants such as dyes are difficult to biodegrade. In this study Fenton, photo-Fenton and photocatalysis were used to degrade methylene blue dye in the presence of copper oxide catalysts. The copper oxide catalysts were prepared with a precipitation reduction method. The effect of different preparation parameters on the catalyst properties and catalytic activity were investigated. The reducing agents, ascorbic acid (ASC, C6H8O6), hydrazine (N2H4), sodium boron hydride (NaBH4) and glucose (C₆H₁₂O₆) could be used to obtain the desired Cu2O phase. ASC, N2H4 and NaBH4 were able to reduce copper (II) to copper (I) at room temperature whereas glucose required a higher reduction temperature. Stoichiometric amounts of the reducing agents ASC, N2H4 and glucose and double the stoichiometric amount of NaBH4 were required to obtain Cu2O. A further increase in the amounts of NaBH4 and N2H4 resulted in the formation of copper metal (Cu (0)). High amounts of ASC did not over-reduce the copper. ASC also functioned as capping molecule and anti-oxidant preventing the oxidation of the Cu2O to CuO in air after preparation. Hydrazine was thus not able to protect the Cu2O against oxidation. The SEM results showed that an increase in the amount of the precipitating agent, NaOH, resulted in an increase in the particle sizes. The particle shapes changed from spherical to cubic when a high amount of NaOH was used with hydrazine as reducing agent. Smaller particle sizes were obtained when CuCl2 was used instead of CuSO4 and Cu(NO3)2. Larger crystallites formed when the preparation temperature was increased from room temperature to 100°C with glucose as reducing agent. TEM and XRD analyses showed that the micro-particles seen in SEM analyses are made up of nano-particles. The catalysts were not active for photocatalysis which may be explained by the oxidation of these nano-particles to form the photocatalytic inactive CuO. The catalysts were shown to be active for Fenton and photo-Fenton degradation. The addition of graphene and activated carbon to the Cu2O catalysts were detrimental to the catalytic activity. The percentage degradation of methylene blue by the Fenton reaction increased with an increase in the BET surface area from 1.5 m2/g to 10 m2/g and a further increase in the surface area resulted in a decrease in the percentage degradation. A direct correlation between the Fenton catalytic activity and the pore size were found which indicate that the reaction was mass transfer limited.
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    Plasmon catalyst dispersed on carbonised pinecone for enhanced degradation of organic contaminants
    (Vaal University of Technology, 2020-11) Olalekan, Sanni Saheed; Viljoen, Elvera, Dr.; Ofomaja, Augustine, Prof.
    Aromatic organic contaminants are difficult to biodegrade, and thus effective green technologies are required to remove these pollutants from the ecosystem. Tetracycline antibiotic, an organic water pollutant, can be degraded by heterogeneous photocatalysis using an appropriate catalyst, with capability in converting the visible light energy into active species. The thesis focused on silver nanoparticles anchored on silver bromide (Ag/AgBr) as a plasmonic catalyst dispersed on activated carbon (ACK), were used as a photocatalyst (AABR-ACK) in tetracycline removal. The aim is to develop a catalyst that is active in low intensity visible light, whilst the addition of activated carbon will increase the light absorption and separate the charge pairs, after the photocatalyst has been excited by the visible light. The activated carbons were derived from pinecone pyrolyzed in a microwave. The pinecone mass to potassium hydroxide impregnation ratio and microwave pyrolysis time influenced the activated carbon properties. An impregnation ratio of 2.24 and microwave pyrolysis time of 16 minutes at constant microwave power of 400 W yielded the activated carbon with the best-developed porous structure and electrochemical properties. This activated carbon was used during the optimisation of the Ag/AgBr activated carbon (AABR-ACK) catalysts preparation using a thermal polyol precipitation method and response surface methodology. The most active catalyst was the AABR-ACK 11 obtained by a preparation temperature of 140 ºC, time (17.50 minutes), mass of surfactant and activated carbon (0.26 g and 0.03 g) respectively. This catalyst had an ordered nanospheres morphology, reduced electron-hole recombination rate, better electrochemical properties and exhibited enhanced activity on the tetracycline antibiotic removal in comparison to other Ag/AgBr activated carbon catalysts. A percentage degradation of 92% was obtained in 180 minutes were obtained with the AABR-ACK 11 catalyst. The photocatalyst prepared using the best activated carbon derived from pinecone developed in this study was compared to photocatalysts prepared using commercial activated carbon and biochar. The Ag/AgBr activated carbon catalysts using pinecone-derived activated carbon degraded the tetracycline to 92%, which is significantly higher than the percentage degradations (80% and 74%) for the catalyst prepared using commercial activated carbon and biochar catalysts respectively. The higher activity of the Ag/AgBr activated carbon catalysts using pinecone-derived activated carbon was due to the conductive attributes of the catalyst support for accelerated transfer of photo-induced electrons. The Ag/AgBr activated carbon catalysts using pinecone- derived activated carbon also exhibited better performance on tetracycline removal when compared to photocatalysts reported in literature. Two catalyst preparation methods, thermal polyol and deposition precipitation, were compared. The thermal polyol method yielded a more active catalyst for the degradation of the tetracycline in comparison to the deposition precipitation method. The degradation reaction conditions such as pH, light intensity and degradation temperature influenced the rate of the reaction. The highest rate of degradation was obtained at a pH of seven, white light and 40 ºC temperature. The intermediate products formed because of hydroxylation, deamination, demethylation and dehydration during the photocatalytic degradation of tetracycline antibiotics were identified using liquid chromatography mass spectrometer. Quenching experiments with hydroxyl, hole, and superoxide anion species showed that the most important radical responsible for the tetracycline degradation was the superoxide anion radical.
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    Development of a sensitive electrochemical sensor based on carbon dots and graphitic carbon nitride for the detection of 2-chlorophenol and arsenic (III) in water
    (Vaal University of Technology, 2021-02) Moundzounga, Theo Herman Gael; Oseghe, E. O., Dr.; Peleyeju, M. G., Dr.; Ofomaja, A. E., Prof.; Klink, M. J., Dr.
    The presence of organic and inorganic pollutants in aqueous environments is one of the major challenges confronting man. It is therefore important to develop sensitive, versatile and cheap techniques for their detection. Arsenic (III), 2-chlorophenol (2-CP) and sulfamethoxazole (SMX) are priority pollutants that pose health threats to humans and animals. This study was thus aimed at exploring two promising carbon nanomaterials as electrode modifiers for the electrochemical sensing of arsenic (III), 2-CP and SMX in water. Glassy carbon electrode (GCE) was modified with a nanocomposite of carbon dots (CDs) and graphitic carbon nitride (g-C3N4) and used as a sensor for the analytes in aqueous media. The CDs was prepared by a facile one-pot hydrothermal method using pine cone as the carbon source; g-C3N4 and g-C3N4/CDs nanocomposite were prepared via the microwave irradiation heating method. CDs, g-C3N4 and g-C3N4/CDs were dropped-dried on the surface of bare GCE. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the prepared materials. GCE, g-C3N4/GCE, CDs/GCE and g-C3N4/CDs/GCE electrodes were electrochemically investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) using a ferrocyanide [Fe (CN) 6]3-/4- redox probe. The current and the reversibility of the redox probes were enhanced in the presence of modifiers. The electrochemical behavior of arsenic (III), 2-CP and SMX on different electrodes (GCE, CDs/GCE, g-C3N4/GCE and g-C3N4/CDs/GCE) were investigated by differential pulse voltammetry (DPV) under optimized conditions in a phosphate buffer solution (pH 7.6, 6 and 5 for 2-CP, As (III) and SMX respectively). The results demonstrated that the g-C3N4/CDs/GCE electrode significantly enhanced the oxidation peak current of all three analytes. The detection sensitivity of the analytes was greatly improved, suggesting that this new modified electrode has great potential in the determination of trace level of arsenic (III), 2-CP and SMX in water. The oxidation peak currents displayed a linear relationship to concentrations for 2-CP (0.5 - 2.5 μM, R2=0.958, n=5), arsenic (III) (2 - 10 μM R2=0.978, n=5) and SMX (0.3 - 1.3 μM R2=0.9906, n=5). The detection limits of 0.62 μM, 1.64 μM and 0.10 μM were obtained for 2-CP, arsenic and SMX, respectively. Phenol and 4-chloro-3-methyl-phenol were found to interfere with the detection of 2-CP, while, Cu2+, Zn2+, Pb2+ and Cd2+ were the only significant ions that interfered with the electrochemical detection of arsenic (III). EDTA was used as a ligand to mask the interference effects of copper, cadmium, lead and zinc on arsenic sensing. The modified electrode (g-C3N4/CDs/GCE) was used to determine arsenic, 2-CP and SMX in spiked tap and effluent water samples by the standard addition method and the results showed percentage recoveries varying from 93-118% for 2-CP, 98-100% for arsenic and 80-105% for SMX. The outcomes of this study established that the nanocomposite material represents an easy and sensitive sensing platform for the monitoring of arsenic (III), 2-CP and SMX in aqueous media.
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    Adsorption of Cr(VI) by iron oxide functionalized polyethyleneimine (PEI) coated activated carbon-silica composites
    (Vaal University of Technology, 2020-12-14) Qhubu, Mpho Cynthia; Nomngongo, P. N., Prof.; Pakade, V. E., Prof.
    Water scarcity due to limited resources and pollution of the little available water by organic and inorganic contaminants remains as one of the critical issues of the 21st century. Several treatment methods have been developed, with some being used successfully at industrial scale but many challenges including secondary sludge generation, high operation costs, high maintenance costs and high energy input were observed. In this study, the adsorption process was explored as an effective means for the removal of Cr(VI) ions from aqueous solution due to its economic feasibility and use of abundantly available adsorbents. Amongst the many available adsorbents, this work focused on exploring functionalized activated carbons (ACs) as adsorbents for Cr(VI) ions due to their favorable adsorption characteristics which involve large surface area, high porosity, and high radiant stability. The iron oxide functionalized polyethyleneimine activated carbon-silica composites were prepared through co-precipitation of Fe(II) and Fe(III) over Macadamia activated carbon to form the AC-Fe3O4 co-shell which was reacted with tetraethylorthosilicate (TEOS) and the polyethyleneimine (PEI). The different adsorbents prepared were labelled AC-Fe3O4, AC-Fe3O4-SiO2 and AC-Fe3O4-SiO2-PEI. The adsorbents were further characterized using elemental analysis (CHNS), thermo gravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET), transmission electron spectroscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). FTIR displayed successful attachment of Fe3O4 and SiO2 with bands at 404 and 786 cm-1 being assigned to the asymmetric vibration of Fe-O and Si-O-Si while the asymmetric stretch of Si-OH is observed at 1066 cm-1. XRD showed the presence of magnetite particles in the adsorbents confirmed by the JCPDS 00-019-0629. EDS revealed the presence of Fe, Si, and N atoms which can relate to successful incorporation of the desired functional groups. Each of these materials were evaluated for their Cr(VI) ion removal through batch adsorption experiments where one parameter at a time was varied while all others were fixed. The parameters investigated included the effect of pH, contact time, initials Cr(VI) concentration, adsorbent dosage concentration and temperature. The optimum conditions were obtained at pH 3, initial concentration 2.5 mg/L, contact time of 120 min for AC-Fe3O4-SiO2-PEI. The optimization of each parameter was done in order to determine the conditions in which the adsorbents work best in the uptake of Cr(VI). All the three studied adsorbents showed acceptable adsorption performance for the removal of Cr(VI) from aqueous solutions. Adsorption isotherms studied confirmed that the adsorption data in all the three adsorbents fitted well into the Langmuir isotherm, demonstrating a homogeneous monolayer coverage. Regarding the kinetic studies, the adsorption data were best described by the pseudo-second order rate model with R2 values of 0.974, 0.974 and 0.962 for AC-Fe3O4, AC-Fe3O4-SiO2 and AC-Fe3O4-SiO2-PEI, respectively. The adsorption capacity observed from the present study (6.62, 3.92 and 5.48 for AC-Fe3O4, AC-Fe3O4-SiO2 and AC-Fe3O4-SiO2-PEI, respectively) were satisfactory and suitable as compared to those reported in literature. Thermodynamics data of the adsorption processes revealed a feasible spontaneous endothermic adsorption process which also confirmed that the reaction process occurred through chemisorption.
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    2,2-Dithiobis(benzothiazole) complexes (Cd and Ni): Precursors to nanoparticles and electrochemical properties and interactions with Rhodamine B
    (Vaal University of Technology, 2021-10-13) Mabaso, Busisiwe Dagracia; Moloto, N., Prof.; Moloto, M. J., Prof.
    The ligand 2, 2-dithiobisbenzothiazole and it metal complexes have been a subject of interest in various fields but they have found to exhibit remarkable and prevalent biological and pharmacological activities. The ligand tends to coordinate to complexes through the sulfur atom and hence the metal-sulphide bond are good precursor to generate metal sulfide nanoparticles using single-source precursor route. The complexes are generally prepared by reflux for 1 to 2 hours depending on the solvent used to produce very stable solid products and some form in crystalline form. All the prepared nickel and cadmium complexes were characterized using techniques such as elemental analyzer, IR, 13C NMR spectroscopy and thermogravimatric analysis. The data obtained from the spectroscopic analysis was consistent of the coordination of the ligand with the metal ions through the sulphur atoms of the 2,2-dithiobisbenzothiazole moiety. The thermal analysis of the prepared complexes gave a final residue of metal sulphide for both metal complexes. Characterization techniques showed the formation of bidentate complexes for both nickel complex and cadmium complex. The prepared complexes were then used to synthesize metal sulphide nanoparticles .The nanoparticles were prepared by thermal decomposition method of the single source precursor in a solution of oleylamine (OLA). Two different parameters were investigated temperature and time to study their effect on the size and shape of the nanoparticles. The synthesized nanoparticles were characterized using techniques such as UV-Vis spectroscopy, photoluminescence spectroscopy, and X-ray diffraction analysis and transmission electron microscopy. The temperatures of the reaction have a significant effect on the rate of the reaction that will affect the size and shape of the nanoparticles. This effect was confirmed by the optical properties of the synthesized nanoparticles prepared at different reaction temperatures. The spectra shows that absorption maximum and band edge shift to lower wavelength as the temperature of reaction was progressively increased. This trend is associated to the decrease in particles size of the prepared nanoparticles. TEM images further confirmed that the particles size of the prepared nanoparticles was progressively decreased as the temperature was increased. The time of the reaction is one of the most significant factors in the synthesis of the nanoparticles. The investigation of the time of the reaction yield results that depicted that with increase in time of the reaction, the band edge increases, but relatively at short wavelength to the bulk. Hence, the band edges of the nanoparticles were blue shifted significantly to the bulk. The results show that with an increase in the time of the reaction, the nanoparticles increases in their size due to Ostwald ripening. The optimum complexes and optimum nanoparticles were used to further study their electrochemical properties using cyclic voltammetry and electrochemical impedance spectroscopy (EIS) graphs were fitted using the randles circuit and they confirm that the NiS nanoparticles GCE greatly increase the electron transfer rate, probably due to the nanostructured surface property of the NiS nanoparticles. Differential pulse voltammetry (DPV) was used to study the electrochemical behavior and the DPV showed that the current response of Rhb was higher for the optimum temperature NiS nanoparticles compared to all the materials used. There was an increase in the Rhb current response with an increase in pH and pH 7 was used as the optimum pH when Ni- complex was used as a modifier and pH 8 was used as optimum when NiS nanoparticles were used as a modifier. Effect of concentration showed that the NiS nanoparticles for the optimum temperature had a wide linear range and a low detection limit. The method has good accuracy, acceptable precision, and reproducibility. This method provides a novel electrochemical method for determination of RhB.
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    Incorporation of silver nanoparticles and eucalyptus oil onto electrospun hemp/PVA nanofibres and their antibacterial activity
    (Vaal University of Technology, 2021) Mogole, Lebogang; Viljoen, Elvera, Dr.; Omwoyo, Wesley Nyaigoti, Dr.; Moloto, Makwena Justice, Prof.
    The world is continuously losing the battle against superbugs (resistant bacteria towards commonly used antibiotics), hence there is an urgent need to develop novel antibacterial agents. In this study, green synthesized silver nanoparticles (AgNPs) and eucalyptus oil, were incorporated into the polymer blend fibres of polyvinyl alcohol (PVA) and cellulose nanocrystals (CNC’s). Various techniques were used to characterize the AgNPs, PVA/CNC polymer fibres, and PVA/CNC incorporated with AgNPs/eucalyptus oil. The morphology of AgNPs synthesized using an increasing concentration of the Citrus sinensis peels (CSP) extract was obtained from transmission electron microscopy (TEM). AgNPs synthesized using 1 and 2 % m/v (CSP) were agglomerated and whereas those synthesized using 3 % m/v of the extract were spherical with an average particle size 10 ± 1.2 nm. UV/Visible absorption spectra for all the synthesized AgNPs exhibited a surface plasmon resonance (SPR) peak at around 400 nm which is a characteristic peak of silver. Significant shifts in the absorption peaks or maxima were observed to signify changes in the shape and size of the nanoparticles. Scanning electron microscopy (SEM) was used to study the morphology of the fabricated polymer fibres. The Addition of CNC’s to PVA resulted in an increase in fibre diameter due to an increase in viscosity of the solution. An increase in the concentration of silver nanoparticles and the eucalyptus oil in the PVA/CNC resulted in a decrease in fibre diameter due to an increase in conductivity of the material. The fibres with AgNPs were smooth while the ones with the eucalyptus oil were beaded. X-ray diffraction (XRD) showed the presence of the AgNPs in the polymer fibres and Fourier transform infrared (FTIR) showed the presence of the functional groups that are available in the eucalyptus oil. The antibacterial efficiency of the PVA/CNC incorporated with AgNPs, eucalyptus oil, and the mixture of AgNPs and the eucalyptus oil was investigated using S. aureus and K. pneumoniae. All the materials showed significant inhibition of the growth of the selected bacterial strains. PVA/CNC polymer fibres incorporated with AgNPs showed higher antibacterial activity compared to PVA/CNC polymer fibres incorporated with eucalyptus oil.
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    Incorporation of metal (silver, copper, iron) chalcogenides (oxide, selenide) nanoparticles into poly(methyl methacrylate) fibers for their antibacterial activity
    (Vaal University of Technology, 2020) Sibokoza, Simon Bonginkosi; Moloto, N., Prof.; Mthunzi, F., Prof.; Moloto, M. J., Prof.
    Nanoscience receives a lot of attention in the 21 century and is one of the most advancing technology in our days. It provides many new and advanced technological opportunities. This field involves many disciplines which include chemical, physical, and biological related fields. The advancement of nanoscience makes life to be better and bring about new inventions which can solve many problems in our day to day life. Although there are reservations about the use of these materials in other fields. Some researchers believe that these materials can be a problem to the environment and humanity at large. Therefore, more research needs to be done to fully understand these materials. Polymer science is another field that has been advancing every day. Many problems in our lives require material which have properties from nanomaterials and polymers. The combination of these technologies can leads to new materials which have many possibilities in solving most problems. Some researchers have taken advantage of these two powerful fields and merge them. There has been a lot of work done that involves combination of nanotechnology and polymer science. The current project is an initiative to manufacture nanofibers. These fibers are prepared using polymer solution mixed with metal oxide and metal selenide nanomaterials. The polymer solution is incorporated with nanoparticles and electrospunned to make nanofibers. The electrospinning afford the material prepared to be at nanoscale. The fact that the material formed is at nanoscale opens many possibilities to be used in various fields. The study is about fabrication of polymer nanofibers embedded with metal chalcogenide nanoparticles. The metal oxide and metal selenide nanoparticles were prepared using complexes. These complexes contain both the metal and the chalcogenide of interest. The complexes are prepared from oxygen-based (urea), and selenium-based (diphenyldiselenide) ligands. The urea complexes co-ordinates with metal using oxygen for iron, however in silver complexes both nitrogen and oxygen are used. These complexes allow easy control of reaction parameters, and thermal decomposes to form metal oxide, metal selenide, and metal. The complexes are very stable and decomposes at about 200 °C. These compounds are thermal decomposed to form metal chalcogenides, and metal nanoparticles. The complexes are characterized with FTIR, TGA, and elemental analysis. The metal chalcoginedes (copper oxide, iron oxide, silver oxide, copper selenide, iron selenide, and silver selenide) nanoparticles were prepared using thermal decomposition of a single source (complexes or metal salts). The prepared chalcogenides nanoparticles have good absorption and emission properties consistent with small sizes. These nanoparticles are composed of various phased and stoichiometry. Some metal chalcogenides have a mixture of stoichiometry and phase. The metal chalcogenides nanoparticles are dominated by spheres, and other shapes such as rods. These metal chalcogenides have a particles size in the range of 1-36 nm. The metal chalcogenides nanoparticles were tested against bacteria and fungi. These nanoparticles show highest activity in gram positive compared to gram negative bacteria. Metal oxide nanoparticles show the highest activity compared to metal selenide. All the metal chalcogenides show the highest against fungi. The nanoparticles are able to inhibit the fungi at lowest concentration. The nanoparticles are characterized with various instruments which includes UV-Vis, PL, XRD, and TEM. Nanofibers of poly(methyl methacrylate) (PMMA) incorporated with metal selenide and metal oxide nanoparticles were prepared by electrospinning. The nanofibers incorporated with metal chalcogenide are more thermal stable than PMMA nanofibers. Therefore, incorporation of metal chalcogenides nanoparticles leads to more thermal stability nanofibers. The PMMA are coordinated to the metal oxide and metal selenide through carbonyl oxygen atom. The PMMA incorporated with metal oxide and metal selenide leads to the formation of nanofibers with uneven surface with a diameter in the range of 30 to 200 nm. The prepared fibers are characterized using FTIR, TGA, SEM.
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    Zein, Collagen and PVA polymer fibre blends embedded with metal (Mn and Fe) oxide nanoparticles for wastewater treatment
    (Vaal University of Technology, 2020-09) Kubheka, Nompumelelo Sharol Mbali; Mkhumbeni, N.; Moloto, M. J., Prof.
    The polymer and their blended fibres provide good surface and intermolecular chemistry that bring additional functionalities and structural changes that can be adapted for new usages. Natural polymers are known to possess desirable qualities in terms of biocompatibility and biodegradability. The natural polymers are chosen due to their abundance but have difficulties in the preparations hence the addition of a synthetic polymer is vital. An important property of the polymer blended fibres is its miscibility which affects the mechanical properties, the morphology and degradation. Metal oxide nanoparticles embedded into polymer blended fibres enhances the performances of the polymer blended fibre permeability, selectivity, strength, and hydrophilicity. This study reports on the synthesis and characterization of zein, collagen nanofibres, zein/PVA fibre blends, iron oxide, manganese oxide nanoparticles, Fe2O3/zein /PVA and Mn2O3/zein/PVA fibre nanocomposite blends. The zein nanofibres and zein/PVA fibre blends were electrospun using electrospinning technique. Parameters such as the concentration and voltage were investigated. These parameters had an effect on the fibre morphology. The electrospun zein nanofibres and zein/PVA fibre blends were characterized using scanning electron microscopy (SEM), UV-Visible spectroscopy, Photoluminescence (PL), X-ray diffraction (XRD), Fourier transformer infrared (FTIR) spectroscopy and Thermal gravimetric analysis (TGA). The SEM results illustrated that an increase in the concentration of zein nanofibres improved the morphology of the fibres into ribbon like shape and had an effect on the average diameter size. The addition of PVA into zein nanofibres enhanced electrospinnabilty and the mechanical strength of zein was dependent on the presence of PVA. The optical properties, XRD, FTIR and thermal studies confirmed that zein/PVA (80/20) blend weight ratio was miscible and the other blend weight ratios remained immiscible, this was due to stronger interaction of hydrophilic performance of zein and PVA through hydrogen bonding. Therefore, fibre blend weight ratios of zein/PVA (90/10, 80/20, 70/30, 60/40 and 50/50) were successfully fabricated. The optimisation of collagen nanofibres favoured electrospraying instead of electrospinning hence collagen nanofibres could not be fabricated. Iron oxide nanoparticles was synthesized using hydrothermal method and manganese oxide nanoparticles was synthesized through co-precipitation method. The TEM results revealed well defined shapes of metal oxide nanoparticles illustrating that the increment of temperature had an influence on the crystallinity and particle size of 𝛼-Fe2O3 , 𝛼-MnO2 and 𝛼-Mn2O3 nanoparticles. The XRD confirmed the crystalline pattern of the metal oxide nanoparticles were of rhombohedral 𝛼-Fe2O3 structures (JCPDS 00-033-0664), cryptomelane phase 𝛼-MnO2 (JCPDS No. 29-1020) and orthorhombic crystalline phase of 𝛼-Mn2O3 (JCPDS No. 04-007-088). The metal oxide nanoparticles were thermally stable. Three different concentrations (4.25 wt%, 4.75 wt% and 5.25 wt %) of 𝛼-Fe2O3 and 𝛼- Mn2O3 were embedded onto zein/PVA (80/20) fibre blends and electrospun. The SEM, optical properties, XRD and TGA confirmed that the embedment of metal oxide nanoparticles enhanced the zein/PVA fibre blends performance, mechanical strength and resistance to wear therefore 5.25 wt% of 𝛼-Fe2O3/zein/PVA and 𝛼-Mn2O3/zein/PVA were explored further for the adsorption of chrysoidine G removal from wastewater. The adsorption studies of zein/PVA (80/20), 𝛼-Fe2O3/zein/PVA and 𝛼-Mn2O3/zein/PVA were carried out in a batch system on the effects of contact time, pH, initial concentration and adsorbent dosage. All the nanoadsorbents could rapidly reach adsorption equilibrium within 30 min at room temperature. The maximum removal efficiency of chrysoidine G of zein/PVA, 𝛼-Mn2O3/zein/PVA was higher than 𝛼-Fe2O3/zein/PVA. The dye adsorption equilibrium data were well-fit with Langmuir isotherm rather than Freundlich isotherm. The comparison of kinetic models revealed that the overall adsorption process was described well by pseudo second-order kinetics. The polymeric materials were cost effective hence regeneration studies were implemented for three cycles. These nanoadsorbents are easily available and are expected to be economical.
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    Preparation and application of pine-magnetite composite grafted with functional vinyl monomers for removal of dyes from single and binary solutions
    (Vaal University of Technology, 2021-05) Mtshatsheni, Kgomotso Ntombizodwa Gina; Naidoo, E. B., Prof.; Ofomaja, A. E., Prof.
    Water is a basic resource to mankind. The environment is deteriorating daily due to industrial pollution of water resources. Industrial effluents containing organic pollutants such as dyes are undesirable even at low concentrations in the environment. Natural biomaterials have been applied as adsorbents for dye removal from water systems, however, their application has been limited by their low adsorption capacity. Much attention has been focused on the chemical modification of natural biomass via grafting processes. The modification of natural polymers by graft copolymerization is a promising technique since it functionalizes a biopolymer thus imparting desirable properties. The purpose of the study was to prepare and optimize the working conditions for the pine-magnetite bionanocomposites (PMC) as adsorbents and as photocatalysts modifiers. First, this work focuses on the synthesis and optimization of reaction variables in the preparation of PMC for the removal of methylene blue (MB). The thesis also explores the synthesis of acrylamide and acrylic acid-grafted PMC, resulting in the formation of acrylamide-grafted PMC (GACA) and acrylic acid-grafted pine-magnetite bionanocomposites (GAA), respectively. The grafting of functional groups such as –CO, –NH2 onto cellulose from acrylamides is also explored in detail. The adsorption conditions optimized were used to investigate the adsorption efficiency of GAA and GACA on MB. Finally, the application of PMC and GAA as modifiers for amorphous TiO2 and N-doped TiO2was carried out. The photocatalytic bionanocomposites from PMC (namely PMC–a-C,TiO2 and PMC–a-C,NTiO2) and those from GAA (labeled GAA–a-C,TiO2 and GAA–a-C,NTiO2) are compared by their photocatalytic efficiency on the degradative removal of an alkaline dye mixture formed from Reactive red 120 (RR 120) and Rhodamine B (Rh B). The synthesis procedure for PMC involved treating pinecone biomass with 0.15 M NaOH solution to remove unwanted plant extracts and the subsequent coating of the treated pinecone with iron oxide magnetic particles through a co-precipitation method. The variables used for the experiments were volume of NH4OH (5 to 40 cm3), reaction temperature (40 to 100 °C), effect of time (15 to 60 min) and mass (1.0 to 3.5 g). The PMC and acrylic acid grafted pine-magnetite composite (GAA) were probed for structural morphology and surface properties using various surface characterization instrumental techniques. Strong chemical interactions between pinecone magnetite and acrylic acid were demonstrated by thermogravimetric (TGA), differential thermal analysis (DTA) and X-ray photoelectron spectroscopy (XPS) for these unique bionanocomposites as such suggesting high chemical stability. Grafting acrylic acid was shown by XPS to form polyacrylic acid on the surface of the bionanocomposites and thus capping the surface groups. Significant differences in size were shown by transmission electron spectroscopy (TEM) and scanning electron microscopy (SEM); i.e., smaller particle sizes (Ave = 13.0 nm) for GAA and slightly larger for PMC (Ave = 14.0 nm). Brunauer Emmett Teller (BET) surface analysis demonstrated a larger surface area, pore volume and pore diameter (59.9 m2.g-1, 0.2254 cm3.g-1 and 28.14) for GAA compared to PMC. These characteristics coupled with the point of zero charge for GAA (pHpzc = 6.8) were critical in enhancing the efficiency of GAA adsorption of MB at pH 12 and further enable GAA to have a higher desorption efficiency of up to 99.7% after four cycles of washing with 0.10 M HCl. The adsorption kinetics and isotherm studies indicated that the adsorption process follows the pseudo second order kinetics and Langmuir isotherm respectively. The adsorbent also showed improvement in the adsorption capacity and reusability promising to be used for the removal of dyes in a prototype scale. GAA and MB adsorption mechanism was confirmed to be through intra particle diffusion. The overall performance of the GAA bionanocomposites is hinged on the formation of polyacrylic acid on the surface, its structural morphology, and the enhanced surface properties. Most importantly, the plant-based materials (lignin and cellulose) provide an environment that is rich with surface (–COOH and –OH) groups for the attachment of the magnetite nanoparticles while the polyacrylic acid stabilizes the magnetite onto the pinecone nanoparticles while reducing the point of zero charge for increased adsorption of cationic species. The photocatalytic bionanocomposites were fabricated from the adsorptive bionanocomposites using a simple solgel process in which ~10 wt.% of PMC and GAA, respectively, were used as a starting agent. Titanium butoxide was used as a precursor, acetylacetone as a dispersant and ethylene diamine as a nitrogen source. Using this procedure, amorphous carbon-doped titania (a-C,TiO2) and amorphous carbon and nitrogen co-doped titania (a-C,NTiO2) were fabricated except that the biopolymer was not added. Two sets of amorphous titania bionanocomposites were fabricated. One set was the nitrogen doped forms that had been modified with PMC and GAA (PMC–a-C,TiO2 and GAA–a-C,NTiO2). The other set of photocatalytic bionanocomposites produced in this work were without nitrogen (PMC–a-C,TiO2 and GAA–a-C,TiO2). TEM and SEM micrographs showed that all the photocatalysts consisted of globular, smooth aggregates of nanosized a-CTiO2 and a-C,NTiO2 which decreased in size with N-doping and the incorporation of GAA and PMC to as low as <30 nm. Surface chemical analysis through FTIR, XPS and EDS confirmed the presence of C, O, Ti and N (for the N-doped photocatalysts). In addition, it was demonstrated that N-doping into TiO2 had taken place, albeit with most of the N incorporated as organic nitrogen. It was further demonstrated that because of the absence of high temperature calcination, the process chemicals played a significant role in doping the photocatalysts with carbon resulting in the promotion of photocatalytic activity for a-C,TiO2 to the point of surpassing that of, a-C,NTiO2 and all the PMC-modified photocatalytic bionanocomposites. a-C,TiO2 had an overall 94% removal of the dyes, Rhodamine B (RhB) and Reactive red 120(RR 120), under UV illumination. The benefit of co-doping a-TiO2 with C, N and the biopolymers was realized with the incorporation of GAA as a modifier. The result was 97% removal of the dyes by GAA–a-CTiO2 and 99% for GAA–a-C,NTiO2. It was further observed that the degradation of the binary mixture of the dyes (RhB and RR 120) proceeded through the zero order kinetics for the a-C,TiO2 based photocatalysts and first order kinetics for the N-doped photocatalysts. The work, has, therefore demonstrated the applicability of plant-based biopolymers in the fabrication of nanoadsorbents and nanophotocatalysts. While the photocatalytic degradations were carried out under UV-light, there still remains a number of possible avenues that researchers can build on to improve the visible light-driven photocatalytic bionanocomposites. The research work has proven the effectiveness of novel pinecone magnetic nanoparticle materials and TiO2-based photocatalyst for the degradation of undesirable dyes from wastewater.
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    Synthesis, characterisation, and application of conjugated polyene modified TiO2 photocatalysts for the treatment of selected pharmaceuticals in water
    (Vaal University of Technology, 2020) Awofiranye, Olayinka Oladimeji Samuel; Naidoo, E. B., Prof.; Modise, S. J., Prof.
    This research has investigated the effects of conjugation on the visible light absorption capacity of polyene modified TiO2 nanoparticles as well as the efficiency of these nanoparticles for the mineralisation of acetaminophen (APAP), a non-antibiotic and chloramphenicol (CAP), an antibiotic pharmaceutical compound (PC) which are commonly used worldwide. The efficiency of polyene modified TiO2 (CPE-TiO2) compared with bare TiO2 was further assessed for the mineralisation of the selected PCs under visible light. To achieve this aim, the synthesised nanoparticles were appropriately characterised and tested for the photocatalytic degradation of acetaminophen (APAP) and chloramphenicol (CAP), under visible light. Furthermore, the mechanism and the kinetics of photocatalytic degradation of the PCs were investigated by using high-performance liquid chromatography (HPLC) to monitor the photodegradation intermediates, e.g. Hydroquinone, p-nitrophenol and oxamic acid. The DRS UV-vis spectra result of the CPE-TiO2 indicated that it has a lower band-gap than bare TiO2 nanoparticles and demonstrated a better absorption ability in the wavelength range of 400-800 nm. This result was further confirmed by other optical analyses, such as electrochemical impedance spectrometry (EIS) and photoluminescence (PL). The analysis indicated a less recombination rate of electron/hole pairs in CPE-TiO2 compared to TiO2. Notably, CPE-TiO2 nanocomposite exhibited higher photocatalytic properties for both pollutants, compared to bare TiO2 under visible light. Importantly, photocatalytic degradation experiments demonstrated that the CPE modified nanoparticles were significantly more efficient for PCs degradation (94.21 % for APAP and 80.47% for CAP) compared to bare TiO2 (27.12% for APAP and 36.12% for CAP). The role of CPE-TiO2 photocatalysis in degrading APAP and CAP was examined by varying experimental parameters such as PC concentrations, catalyst loading and solution pH. All the parameters were observed to influence the degradation of the PCs to some extent, albeit, at optimum conditions, most of these PCs were degraded within 210 minutes of visible light irradiation. A significant relationship between the ionic state (+ve or -ve based on the pH) of the solution and CPE-TiO2 photocatalytic process was observed. For the mineralisation, CPE-TiO2 photocatalysis led to higher oxidation rates compared to direct photolysis and bare TiO2 photocatalysis. The results confirm that the co-existence of multiple bonds in poly-conjugated carbon chains with a reduced band-gap in CPE-TiO2 composite were able to enhance charge separation and migration as well as improve the photocatalytic efficiency. This study has clearly demonstrated that polyene modified TiO2 nanoparticles can be applied to degrade PCs in aqueous solution and offers an attractive option for small-scale pharmaceutical wastewater treatment. However, the complex nature of real effluents with co-existing pollutants and higher levels of organic and inorganic matter may call for possible coupling of a biological process as pre- or post-treatment to improve their biodegradability.