Ruthenium (II) complexes of mixed bipyridyl and dithiolate/thiourea ligands :|bsynthesis, characterization, photophysical and electrochemical studies
- Authors: Nkombi, Pelokazi
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/10134 , vital:35358
- Description: Energy is one of the most important factor to influence human lives. The increased in energy demand as well as the detrimental effects posed by emission of greenhouse gases due to continue use of fossil fuels for electricity generation has led to a renewed focus on energy production using renewable energy sources which are relatively cheap, clean and environmentally sustainable. Among the various renewable energy sources used so far, the Dye Synthesized Solar Cells (DSSCs), a form of photovoltaic device is reported for their better efficiencies despite their low cost of production and ability to work relatively under low light conditions. A recent report on the solar-to-electricity conversion efficiency of a typical DSSC sensitizer made from zinc based porphyrin dye coupled with sintered titanium(IV) oxide as semiconductor was 13 percent. In this study, 2,2-bipyridyl-4,4-dicarboxylic acid (bpydc) was used as mixed ligand and four dithiolate ligands; L1 = dipotassium ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate, L2 = dipotassium bis(ethoxycarbonyl)ethane-2,2-dithiolate, L3 = dipotassium cyanodithio imidocarbonate and L4 = dipotassium 2,2-dicyanoethylene-2,2-dithiolate were synthesized while four alkyl thiourea ligands, L5 = 1,3-dimethyl thiourea, L6 = 1,3-diethyl thiourea, L7 = 1,3-diisopropyl thiourea and L8 = 1-methyl thiourea were purchased and used as supplied without further purification. These ligands were used to prepare eight ruthenium(II) complexes of mixed bipyridyl/dithiolate/thiourea. The compounds were characterised by elemental analysis and spectroscopic techniques, namely: Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR), ultraviolet-visible and photoluminescence (PL). Cyclic voltammetry (CV) and square wave voltammetry (SWV) were used for the electrochemical studies. Photoluminescence and UV-Vis spectroscopies were used for geometric and photophysical studies of the complexes respectively. FTIR spectra confirmed presence of functional groups in ligands and coordination of these ligands to ruthenium(II) ions to form complexes. The UV-Vis confirmed that the Ru(II) dithiolene complexes exhibited square planar geometries while the Ru(II) thiourea complexes gave octahedral geometries, this was deduced from the transitions assigned to the complexes. All the ruthenium(II) complexes synthesized showed photoluminescence properties that are suitable for light harvesting and application for dye-sensitized solar cells. Cyclic and square wave voltammetry show Ru(II) thiourea complexes have better redox properties when compared to Ru(II) dithiolate complexes which is ascribed to ligand strength field possibly due to contribution from the two bonded NCS groups.
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Synthesis, characterization and evaluation of photophysical and electrochemical properties of ruthenium(II) complexes for dye-sensitized solar cells
- Authors: Adjogri, Shadrack John
- Date: 2018
- Subjects: Ruthenium Ruthenium compounds
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/17828 , vital:41363
- Description: Eight series of thirty (30) novel heteroleptic ruthenium(II) complexes were designed, synthesized and spectroscopically characterized, with the following general molecular formulae as [Ru(bdmpmar)(H2dcbpy)(NCS)]+, [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2,+, [Ru(bdmpmar)(vpbpp)(H2dcbpy)]2+,[Ru(H2dcbpy)2(N^)(NCS)]+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2], [Ru(H2dcbpy)(N^)(NCS)3]– and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ where bdmpmar is a tridentate ligand of N,N-bis(3, 5-dimethylpyrazol-1-yl-methyl) aromatic organic compound (such aromatic organic compounds(Ar) are anthranilic acid, 4-methoxy-2-nitroaniline, aniline, toluidine, cyclohexylamine and anisidine), vpdiinp represents a monodentate ligand of 11-(4-vinylphenyl)diindeno[1,2-b:2’,1’-e]pyridine, vpbpp represents a monodentate ligand of 4-(4-vinylphenyl)-2.6-bis(phenyl)pyridine and vptpy represents a tridentate ligand of 4’-(4-vinyl)-2,2’:6’,2’’-terpyridine. Meanwhile, N^ represents any of the monodentate ligands of either vpdiinp or vpbpp and (N^^^) represents any of the monodentate ligands either of vpdiinp or vpbpp or NCS as disclosed in series VIII. The complexes were characterized by conductivity measurement, solubility, melting point, UV-Vis, PL, FTIR (ATR), NMR, Cyclic and square wave voltammetry. Nine chelating ligands, comprising of six (6) tripodal chelating ligands, two (2) vinyl monodentate ligands and one (1) vinyl tridentate ligand, were used for the synthesis of ruthenium(II) complexes ATR-FTIR spectra of all the ruthenium(II) complexes measured as solid samples, exhibited fine resolution IR bands in region between 3473-3438 cm-1 of carboxylic group in H2dcbpy. The bands in the range 3040-2950 cm-1 were ascribed to C-H bond stretching for the CH3 groups. The coordination of NCS group in the sphere of ruthenium(II) complexes related to series I, IV, VI VII and one compound of series VIII was investigated by ATR-FTIR spectroscopy. Bands in the range of 2116-2106 cm-1 and 777-770 cm-1 are ascribed to the respective N=C and the C=S bond stretching vibration which confirms the N-coordination of the SCN group. For all the complexes, the stretching vibration of Ru-N bonding was between 466 and 411 cm-1 due to coordination of the nitrogen atoms of the ligands to ruthenium central metal atom. The introduction of the two vinyl monodentate ligands (vpdiinp and vpbpp) in the coordination sphere of [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2+, [Ru(bdmpmar) (vpbpp)(H2dcbpy)]2+, [Ru(H2dcbpy)2(N^)(NCS)]+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2], [Ru(H2dcbpy)(N^)(NCS)3]– and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ respectively, all related to series II, III, IV, V, VI, VII and two compounds of series VIII ruthenium(II) complexes, has been studied using the 1H and 13C NMR spectroscopy techniques. The 1H NMR spectra of series II-VII and the two compounds of series VIII of the ruthenium(II) complexes show multiplets in the aromatic region above 6 ppm due to the presence of either vpdiinp or vpbpp ligand, situated in different magnetic environment. However, no splitting pattern was observed in series I and part of VIII complexes possibly due to the absence vinyl monodentate subunits (vpdiinp and vpbpp) in series I and one of compound in series VIII ruthenium(II) complexes show no signals of complex splitting patterns. Carbon-13 NMR spectra data of series I to VIII ruthenium(II) complexes show most resonance signals range in the aromatic region of (δ 116.54-199.63ppm) corresponding to the molecular formulation of ruthenium(II) complexes incorporating 4,4-dicarboxy-2,2’-bipyridine, bdmpmar, vptpy, vpdiinp or vpbpp and NCS ligands respectively, depending on the intrinsic ligand variations. Carbon-13 NMR spectra data of series I, IV, VI VII and one compound in VIII show resonance peaks within the range 130-135 ppm are ascribed to NCS ligand confirming the presence of N-coordinated thiocyanate. Cyclic voltammograms of series I-IV and VI-VIII complexes display ruthenium-based oxidative peaks and the pyridines ligand-based reductive peaks. The redox behavior of complexes 4-12, 14-16, 18-20, 24-26 and 30 is dominated by the Ru(II)/R(III) redox couple in region (E1/2 between 0.53 and 1.18) and the pyridines ligand-based redox couples in the region between (E1/2 between −0.25 and −1.45). The photophysical property studies of the Ru(II) complexes are determined through the acquisitions of the absorption spectra, which tends to have profound effect on the short circuit current of DSSC. The absorption maxima were tuned by the introduction and variation of six (6) tripodal chelating ligands, two (2) vinyl monodentate ligands and one (1) vinyl tridentate ligand. From the studies, the results show that series IV, V, VI, VII and VIII complexes of molecular formula [Ru(H2dcbpy)2(N^)(NCS)]2+, [Ru(H2dcbpy)2(N^)2]2+, [Ru(H2dcbpy)(N^)2(NCS)2]2+, [Ru(H2dcbpy)(N^)(NCS)3]2+ and [Ru(vptpy)(H2dcbpy)(N^^^)]2+ respectively, have higher and multiple local absorption maxima near-IR region than the complexes of series I, II and III of molecular [Ru(bdmpmar)(H2dcbpy)(NCS)]2,+, [Ru(bdmpmar)(vpdiinp)(H2dcbpy)]2,+, [Ru(bdmpmar)(vpbpp)(H2dcbpy)]2,+respectively.
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Identification of differentially expressed proteins involved in wheat (Triticum aestivum) resistance against Russian Wheat Aphid (Diuraphis noxia) SA2 using SWATH-MS analysis
- Authors: Ntlokwana, Sitha Emmanuel
- Date: 2020
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/18872 , vital:42888
- Description: Wheat (Triticum aestivum) is the second most-consumed cereal crop in the world, second only to maize. In South Africa it is mainly produced in three provinces; the Free State, Western Cape, and the Northen Cape. The average total land area used for wheat cultivation in these three Provinces, is 533 000 hectares, with a resultant annual production of between 1.3 to 2 million tons. The total wheat requirement in South Africa is currently 2.7 million tons according to the production of wheat guidelines published by the Department of Agriculture, Forestry and Fisheries, which is higher than the total annual production. One of the primary reasons that contribute to the lower production levels is insect and pest infestation, in particular, the Russian wheat aphid (Diurophis noxis), which can result in crop loss of up to sixty percent. Russian wheat aphids (RWA) are invasive insects that feed on the phloem of the plant through their specialised thin stylet-like mouthparts and release toxic agents contained in their saliva during feeding, which disrupt cellular functions inside the host plant. This damage leads to symptoms like; chlorosis, necrosis, wilting, stunting and curling of leaves, also known as leaf rolling. This study aimed to identify differentially expressed proteins in resistant and susceptible wheat (Triticum aestivum) cultivars during Russian wheat aphid Biotype South African 2 (RWA-SA2) infestation, in order to identify proteins involved in the wheat resistant mechanism against RWA-SA2. Two wheat cultivars SST398 (resistant to RWA-SA2) and SST356 (susceptible to RWA-SA2) were used, and a total number of 126 plants were planted and divided according to four different harvest times (Control day 0; day 5; day 7 and day 12). The wheat plants were infested with approximately 10 aphids per plant at the three-leaf stage, and placed within an insect cage inside a growth chamber (Conviron, Winnipeg, Canada) set at 24ºC, light intensity of 352 µmol.m-2.sec-1, ambient CO2 levels (410 ppm) and humidity of 60% with a 16h/8h day/night cycle. Wheat leaves were harvested at various time frames, and total protein extraction was performed. The protein samples were reduced with 10 mM dithiothreitol (DTT) and alkylated with 30 mM iodoacetamide (IAA). Sample clean-up and on-bead trypsin digest were performed on megReSyn Hilic columns, over four hours. The resultant peptides were vacuum dried and resuspended in 2% acetonitrile (ACN) before submitting them to LC-MS/MS (SWATH) for analysis. A total number of 611 proteins were differentially expressed, of which 19 were identified to be involved in the resistance response of wheat, and an additional 20 involved in biotic stress responses. This study showed that reactive oxidative species (ROS) such as hydrogen peroxide and hydroxyl radicals (OH-) play a significant role in the early stages of wheat resistance against RWA-SA2 infestation. They are involved in cell wall strengthening, activation of defence genes, involvement of phytohormone signals such as salicylic and jasmonic acid, which also mediates the systemic defences such as, systemic acquired resistance (SAR), leading to the expression of pathogen-related proteins such as (thaumatin-like proteins, oxalate oxidase, defensin, chitinase, and thionins). Although up-regulation of photosynthesis proteins such as (chlorophyll a/b binding protein, photosystem I and II, rubisco and divinyl chlorophyllide a, and 8 vinyl-reductase) were seen on both infested cultivars (susceptible and resistance), higher numbers of these classes of proteins were identified in the resistance cultivar, suggesting that they also play a critical role in resistance. In conclusion, the SWATH analysis used in this study was able to identify numerous proteins involved in the wheat resistance mechanism against RWA-SA2, most of which have not yet been reported to be involved in either biotic stress or RWA-SA2 resistance responses. Future studies are required to biochemically confirm the involvement of these enzymes and proteins the specific metabolic pathways where they are found, in the wheat resistance mechanism against Russian wheat aphid Biotype 2
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Assessment of the flocculating efficiency of bioflocculant produced by bacillus sp. Aemreg4 isolated from Tyhume river, Eastern Cape, South Africa
- Authors: Ntsangani, Nozipho
- Date: 2016
- Subjects: Flocculants
- Language: English
- Type: Thesis , Masters , MSc (Biochemistry)
- Identifier: vital:11357 , http://hdl.handle.net/10353/d1021324
- Description: Bioflocculants are flocculating substances produced by microorganisms during growth and have recently received considerable attention from researchers; due to their biodegradability, non-toxicity and lack of secondary pollution from degradation intermediates. This study evaluated the efficiency of bioflocculant produced by Bacillus sp. AEMREG4 isolated from Tyhume River. The bacterial identification was through 16S rDNA sequencing; nucleotide sequences were deposited in GenBank as Bacillus sp. AEMREG4 with an Accession number KP406729. The optimum culture conditions for bioflocculant production were an inoculum size of 4% (v/v) and starch as well as yeast extract as sole carbon and nitrogen sources respectively. The addition of CaCl2 enhanced the flocculating activity, at a wide range of pH 4-10 and the highest flocculating activity was reached at an initial pH 8 (80%). A bioflocculant yield of 0.78 g was recovered from 1 L of culture broth. The optimum flocculating activity of 78% was reached at the lowest bioflocculant dosage of 0.1 mg/ml and the presence of divalent cations (Ca2+, Mn2+ and Mg2+) as well as a trivalent cation (Al3+) enhanced flocculating activity. The purified bioflocculant retained more than 70% flocculating activity when subjected to heating at 100 °C for 1 h and maximum flocculating activity of 83% was achieved at both acidic and basic pH values of 3 and 10 respectively. Chemical analysis showed that the bioflocculant is predominantly polysaccharide. The Fourier transform infrared (FTIR) spectrum revealed the presence of carboxyl, hydroxyl and methoxyl groups as the functional moieties and the scanning electron microscopy (SEM) imaging of the purified bioflocculant showed its morphological structure as rod-shaped which contributes to its high flocculating efficiency. The high flocculation activity displayed by this bioflocculant indicates its potential suitability for industrial application.Keywords: Bioflocculant, Bacillus sp. AEMREG4, flocculating activity.
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Synthesis and in vitro biological studies of ursolic acid-based hybrid compounds
- Authors: Khwaza, Vuyolwethu
- Date: 2022
- Subjects: Herbal medicine , Herbs -- Therapeutic use , Antineoplastic antibiotics
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10353/27797 , vital:69689
- Description: Ursolic acid UA, a pentacyclic triterpenoid that is commonly found in many medicinal herbs and fruits, has been identified as a potential source of therapeutic agents because of its potent biological effects, which include its potential anticancer and antimicrobial activities. However, its limited solubility, rapid metabolism and poor bioavailability inhibit its clinical applications. Numerous UA derivatives have been prepared over the past years in an effort to mitigate the drawbacks associated with UA, as new chemical entities for the treatment of various infections. There is very little progress in the discovery of efficient UA derivatives. In this study, a class of ester and amide-linked ursolic acid-based hybrid compounds fused with selected pharmaceutical scaffolds were successfully synthesized using amidation and esterification reactions and tested for antibacterial and cytotoxicity activities. Hybridizing UA with other known pharmaceutical scaffolds has the potential of overcoming its drawbacks. FT-IR, Mass Spectroscopy, and 1H13C-NMR spectroscopy were used to confirm the structures of the synthesized hybrid compounds. Among the tested ester-linked hybrid compounds in Chapter three, compounds 3.14-3.19,3.21, 3.34, 3.31, and 3.30 demonstrated significant antibacterial activities against some tested bacteria, with MIC values of 15.625 μgml. Furthermore, the in vitro cytotoxicity of these hybrids was determined using the MTT assay against three human tumor cell lines MCF7, MDA-MB-231, and HeLa cells. Compounds 3.19 and 3.34 were found to have better cytotoxic activity when compared to ursolic acid, with IC50 values of 46.99 and 48.18 μg ml respectively. Both compounds revealed more promising docking results, presenting favourable binding interactions as well as better docking energy against the MCF 7 protein target compared to the parent compound ursolic acid. In Chapter Four, among the tested amide-linked hybrid compounds, Compounds 4.17 and 4.24 demonstrated significant antibacterial activity against the majority of bacterial strains with MIC values of 15.625 gml. Compound 4.24 exhibited a MIC value of 15.625gmL against BS, SA, PV, KO, PM, and EC. Compound 4.23 was more cytotoxic to HeLa cells than ursolic acid. Furthermore, molecular docking calculations revealed that compound 4.16 strongly binds to the protein epidermal growth factor receptor while e compounds 4.17 and 4.24 showed a strong binding affinity for the methionyl-tRNA synthetase. In both cases, the hybrid compounds showed better conformational fittings in the active site of the targeted proteins as compared to the parent ursolic acid. , Thesis (MSc) -- Faculty of Science and Agriculture, 2022
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Synthesis, characterization, and biological studies of pyrazolone Schiff bases and their transition metal complexes
- Authors: Idemudia, Omoruyi Gold
- Date: 2014
- Language: English
- Type: Thesis , Doctoral , PhD (Chemistry)
- Identifier: vital:11340 , http://hdl.handle.net/10353/d1016068
- Description: Some new acylpyrazolone Schiff bases have been synthesized from the condensation reaction of two acylpyrazolone diketone precursors with phenylhydrazine, 2,4-dinitrophenylhydrazine and sulfanilamide. They have been fully characterized by elemental analysis and spectroscopic techniques (IR,1H and 13C NMR, and mass-spectra). The single crystal structure of the benzoyl derivative acylpyrazolone Schiff bases have been obtained and analyzed by X-ray crystallography technique. Solid state X-ray diffraction revealed a keto tautomer Schiff base in solid state. Mn(II), Co(II), Ni(II) and Cu(II) complexes with the Schiff bases have been synthesized and characterized by elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility measurements, and thermal studies (TGA and DTG). An octahedral geometry around the transition metal ion, consisting of two bidentate Schiff base ligands bonding through the azometine nitrogen and ketonic oxygen have been proposed based on careful interpretation of available analytical and spectroscopic characterization results. Two water molecules as ligands complete the octahedral geometry in all cases. Using the invitro disc diffusion method for screening synthesized compounds against selected gram positive and gram negative bacterial at 40 mg/mL, and the DPPH free radical scavenging methods at 0.50, 0.25 and 0.13 mg/mL, the synthesized Schiff base and metal complexes showed varying biological activities. 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one sul29 fanilamide showed more activity generally, exhibiting a broad spectrum activity against all selected bacterial in some cases. Mn(II), Co(II) and Ni(II) complexes of sulfanilamide Schiff base with the acetylpyrazolone derivative 4-acetyl-3-methyl-1-phenyl-2-pyrazolin-5-one sulfanilamide, exhibited a stronger and very good DPPH radical scavenging activity as good as ascorbic acid on comparing, but not with Cu(II). As such they could be important antitumour candidates.
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Evaluation of some pseudomonas species isolated from Hogsback forest reserve for the production of antibacterial compounds
- Authors: Mkono, Yonela Pelokazi
- Date: 2017
- Subjects: Bacteriology -- South Africa -- Eastern Cape Pseudomonas
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/5961 , vital:29458
- Description: Pseudomonas species are Gram-negative bacteria most abundant in soil and water bodies, with the capacity to thrive in varied environments. They are largely associated with resistant pathogenic bacteria linked to human and plant diseases. Species such as Pseudomonas aeruginosa have been particularly targeted as case studies due to the extremity to which they pose a threat to human health. With more focus directed at using these species for biocontrol and bioremediation purposes, their role in bioactive compound production may be equally important. As the crisis on antimicrobial resistance still persists, the need for effective antimicrobial compounds is ever more urgent and solutions may possibly still be dormant in bacterial species whose potential has not been fully investigated. On a bid to source out potential antimicrobial compound producers, soil samples were collected from Hogback forest reserve in the province of the Eastern Cape, South Africa. For bacterial screening, M1 and R2A agar were used and the cultures grown at 37˚C for a period of seven days. After the presumed Pseudomonas species were identified, antimicrobial production was determined by submerged fermentation method using nutrient broth as media of choice. Active isolates were further studied to determine the optimum conditions which best facilitate for antimicrobial compound production, with parameters such as temperature (25˚C – 40˚C) and pH (4 – 9) considered. The role plasmids play in antimicrobial compound production was also investigated. Each isolate was grown in fermentation media containing Sodium dodecyl sulphate and Ethedium Bromide, at varying concentrations, to facilitate for plasmid curing. With each sample, distinct colonies were identified with varying pigmentations most dominant being a cream colour. The identity of the isolated strains was achieved through sequencing of 16S rDNA. Phylogenetic analysis showed that isolate A16 had 80 percent homology with Pseudomonas plecoglossicida strain P4 and share a close ancestor with isolates Y52 and Y81, also isolate Y89 showed a 90 percent homology with Pseudomonas sp. Co-11a. With the exception of isolate A16, the isolates which were active against Gram-negative bacteria lost activity as the screening processes continued. When looking at temperature variations, isolates Y81 and A16 were highly active with maximum activity observed at 35˚C while Y89 performed best at 25˚C and Y52 showed constant activity across all studied temperatures. The plasmids in all isolates were found to be 48.5 kb in size with the exception of isolate Y89 which was 20 kb. The plasmids were cured at concentrations of (1 mg/ml; 5 mg/ml; 7 mg/ml; 10 mg/ml; 11 mg/ml) SDS and (125 μg/ml; 6.5 μg/ml; 5μg/ml) EtBr. The curing process also showed changes in both the antimicrobial activity of the isolates as well as their physical characteristics. The isolates are the first reported Pseudomonas species from Hogsback forest reserve with the ability to produce antimicrobial compounds which are active against Gram-positive and Gram-negative bacteria. These mesophilic bacteria also show that plasmids do not pay any role in the production of antimicrobial compounds and that the biosynthesis genes are highly likely to be chromosomal borne meaning that the production cannot be linked to horizontal transfer of genes. Therefore, these isolated Pseudomonas species provide a potential reservoir of antimicrobial compounds which may play an important role in the antimicrobial resistance phenomenon.
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Adsorption of antibiotic-resistant bacteria and their cell-free deoxyribonucleic acid harbouring resistance genes in drinking water with metal oxides
- Authors: Tobechukwu, Anthony Eric
- Date: 2022
- Subjects: Metallic oxides , DNA -- Synthesis , Drinking water
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10353/27787 , vital:69494
- Description: Access to cleaner water is essential to human health. The incidence of Antibiotic Resistant Bacteria ARB in drinking water and subsequent proliferation of Antibiotic Resistance Genes ARGs in drinking water is a concern for public health. The free DNA cassette harboring antibiotic resistance gene in drinking water has been linked with impaired public health. The ARGs allows bacteria to develop resistance towards antibiotics while ARB render antibiotics ineffective. Existing drinking water treatment technologies eg adsorption, ozonation and chlorination, have shown different levels of potency in the removal of conventional water pollutant. These technologies, which operating principles is based on oxidation or mass transfer, have been explored to gained an insight into their efficiency in the removal of ARB ARGs in water treatment. In general, methods that functions by mass transfer of the ARB ARGs is more effectively than bacteria oxidation. Consequently, adsorption technology was chosen using common metal oxide adsorbents. The adsorbents ZnOAg CeO2 and Al2O3 were synthesized via the self propagation combustion method. This method was selected because of the purity of the final product and the energy requirement. One of the challenges in the removal of ARB in drinking water is the release of ARGs. To address this concern, five different ZnOAg heterostructures were synthesized for the removal of Enterococci faecium. ZnOAg was chosen because of the bactericidal and bacteriostatic characteristics. The study revealed that the concentration of the precursors influences the microstructures of the adsorbents; however, it did not significantly affect the adsorption efficiency. The maximum adsorption capacity q34.11 CFUg was obtained for Ag1Zn3.5. The kinetic studies revealed that Ag1Zn1 and Ag1Zn2 adsorbents agreed to the pseudofirst-order kinetic equation and adsorbents Ag2Zn1 Ag3.5Zn1 and Ag1Zn3.5 agreed to the pseudo-second-order kinetic equation. Initial tap-water pH range was beneficial for the adsorption and the pH of the treated tap-water was within the WHO tap water recommendation 6.5 – 8.5 whereas the effect of ionic strength, anionic and cationic interference was insignificant in the adsorption of MDREF onto the different heterostructure. Interestingly the MDREF could retain its cell membrane integrity and resistance genes, suggesting that surface adsorption was the primary mechanism for the removal. Cerium IV oxide CeO2 was selected because of high adsorption towards phosphate, backbone base for DNA. To prevent the problem of antibiotic resistance, we have synthesized a CeO2 adsorbent that exhibit highly positive character in a wide pH range, via the simple self-propagation combustion protocol, for the removal of free DNA harboring antibiotic resistance genes. Molecular characterization of the extracted genes showed that the sizes for E. coli and inherent gyrB genes are 147 and 460 bp with a purity between 19 2.0. The XRD SEM TEM, and PZC results of the as-synthesized CeO2 showed an agglomerate of pure cubic-faced centered material and highly crystalline, with a net charge at pH 6.2. Experimental results revealed that the reaction proceeded via pseudo first-order kinetic, and it is governed by electrostatic attraction. The free- DNA solution pH electrolyte, and competing ions impacted on the adsorption process. Further experimental results showed that the as-synthesized CeO2 adsorbent has the potential to be used for the removal of free DNA harboring ARGs from tap-water even under oxic conditions. Alumina Al2O3 is an abundant adsorbent that has also shown high removal capacity towards phosphate. The highly pure synthesized Al2O3 adsorbent exhibit fluid-like behaviour under Scanning Electron Microscope SEM. The XRD pattern corresponds to αAl2O3. The adsorption kinetics was described by pseudo second orderadsorption capacity 11.7 μgg implying chemisorption, which agrees with the electrostatic force of attraction caused by opposing ions. This result was evident by the effect of different ions in the tap water. The synthesized α-Al2O3 has the potential for the removal of cell free DNA harbouring multiply resistant genes. , Thesis (MSc) -- Faculty of Science and Agriculture, 2022
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Surveillance study on pathogenic Acinetobacter species in freshwater environment of the Amathole and Chris Hani District Municipalities, Eastern Cape, South Africa
- Authors: Adewoyin, Mary Ayobami
- Date: 2019-09
- Subjects: Acinetobacter infections , Acinetobacter , Nosocomial infections
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10353/19836 , vital:43257
- Description: This study evaluates the occurrence of medically relevant Acinetobacter species in three rivers, namely; Keiskamma, Tyhume and Great Fish in the Eastern Cape Province, South Africa in one year sampling regime (April 2017 - March 2018). The physicochemical parameters (pH, temperature (TEM), electrical conductivity (EC), total dissolved solids (TDS), salinity (SAL), total suspended solids (TSS), turbidity (TBS), dissolved oxygen (DO) and biological oxygen demand (BOD)) of the water bodies were measured. The presumptive Acinetobacter species recovered from the freshwater resources were recorded and further confirmed using molecular techniques. Similarly, confirmed isolates were subjected to speciation using species-specific primer sets for A. baumannii and A. nosocomialis. Also, virulence genes namely; afa/draBC, epsA, fimH, OmpA, PAI, sfa/focDE, and traT in the two Acinetobacter species were also determined using molecular method. In addition, the antibiogram characteristics of A. baumannii and A. nosocomialis isolated from the water samples were determined using standard methods. The antibiotic susceptibility test was performed using a panel of 12 antibiotics belonging to the aminoglycosides (amikacin, AK and gentamicin, GM), β-lactam/β-lactamase-inhibitor combinations (piperacillin-tazobactam, PTZ), cephems (ceftazidime, CAZ, cefotaxime, CTX, and cefepime, CPM), carbapenems (imipenem, IMI and meropenem, MEM), fluoroquinolones (ciprofloxacin, CIP), folate pathway inhibitors (Trimethoprim/sulfamethoxazole, TS), lipopeptides (Polymyxin B, PB) and tetracyclines (tetracycline, TET). Similarly, antibiotic resistance genes (ARGs) present in the Acinetobacter isolates were investigated including aminoglycoside resistance genes (aacC2, aphA1 and aphA2), β-lactamases resistance genes (blaTEM, blaSHV, blaOXA-1-like, blaCTX-M(GROUP 1), blaCTX-M(GROUP 2), blaCTX-M(GROUP 9), blaVEB, blaGES, blaPER, blaCTX-M-8/-25, blaOXA-48-like, blaVIM, blaIMP and blaKPC), fluoroquinolones resistance genes (qnrA, qnrB, qnrC, qnrD and qnrS), sulfonamide resistance genes (sul1 and sul2), and tetracycline resistance genes (tetA, tetB, tetC, tetM, tetL and tetO). The pH, EC, TDS, SAL, TEMP, TSS, TBS, DO, and BOD for Tyhume River ranged as follows: 7.2-7.7, 125-141 μS/cm, 62-71mg/L, 0.06- 0.07 PSU, 11.3-20.2oC, 30.0-89.6 mg/L, 35.0-96.0 NTU, 8.2-9.8 mg/L, 2.0-4.2 mg/L, while for Great Fish River, the parameters were 8.0-8.2, 274-369 μS/cm, 137-184mg/L, 0.13-0.18PSU, 12.7-22.3oC, 44.3-99.4 mg/L, 48.0-214.0 NTU, 7.8-9.9 mg/L, 3.1- 4.9 mg/L, and at Keiskamma River they were 7.5-7.9, 153.2-285.0 μS/cm, 86-143 mg/L, 0.07-0.14 PSU, 11.0-21.4oC, 27.0- 55.6 mg/L, 31-61 NTU, 8.3-9.8 mg/L, 3.0-6.0 mg/L. A total of 1107 presumptive Acinetobacter spp. were recovered from the rivers sampled of which 428, 370 and 309 isolates were recovered from Tyhume, Great Fish and Keiskamma rivers respectively. However, only 844 was confirmed positive for the genus Acinetobacter and are recovered in the proportions 285 (77 percent), 219 (70.9 percent) and 340 (79 percent) from Great Fish, Keiskemma and Tyhume rivers respectively. Our finding revealed that 410 (48.58 percent) and 23 (2.7 percent) of the isolates were confirmed to be A. baumannii and A. nosocomalis respectively. Also, 308 (75.12 percent percent) A. baumannii and 3 (13.04 percent) A. nosocomialis isolates exhibited one or more virulence genes out of the seven tested, whereas 102 (24.88 percent) and 20 (86.95 percent) of the A. baumannii and A. nosocomialis isolates did not harbour any virulence gene. Additionally, OmpA was the most prevalent (p<0.05) virulence gene found in A. baumannii with 69 (45.10 percent), 52 (50.98 percent) and 77 (49.68 percent) isolates from Great Fish, Keiskamma and Tyhume rivers respectively. The rates of susceptibilities of A. baumannii and A. nosocomialis to the antibiotics followed the order; Piperacillin-tazobactam (72.8 percent ; 73.9 percent), Ceftazidime (70.5 percent ; 91.3 percent), Cefotaxime (16.8 percent ; 17.4 percent), Cefepime (88.5 percent ; 95.7 percent), Imipenem (95.9 percent ; 100 percent ), Meropenem (92.7 percent ; 91.3 percent), Amikacin (97.6 percent ; 91.3 percent), Gentamicin (89.8 percent ; 87 percent), Polymyxin B (84.4 percent ; 91.3 percent), Tetracycline (74.7 percent ; 78.3 percent), Ciprofloxacin (75.9 percent ; 78.3 percent) and Trimethoprim/sulfamethoxazole (74.0 percent ; 73.9 percent) respectively. Both A. baumannii and A. nosocomialis were highly susceptible to all the antimicrobials tested except cefotaxime where 64 percent and 78 percent intermediate responses were observed in the species. At least 10 isolates of A. baumannii were resistant against each of the antibiotics used. The modal multiple antibiotics resistance phenotypes (MARPs) for Acinetobacter spp. was MARP 3 (29.87 percent) and the least was MARP 10 and 11 (2.6 percent each). The antimicrobial resistance index (ARI) was higher at two sampling sites KE2 (0.33) and TY1 (0.22). Similarly, MARI showed that sampling sites KE2 was a hotspot for multidrug-resistant Acinetobacter spp. Of the five classes of ARGs studied, there was a widespread of β-lactamases (blaTEM) in the two Acinetobacter species, followed by sul2, which were detected in 67 (63.2 percent) and 44 (49.4 percent) isolates respectively, across the rivers studied. We conclude that aquatic resources of the study community are important reservoirs of pathogenic Acinetobacter species and antibiotic resistance determinants. The occurrence of clinically-important Acinetobacter species suggests possible contamination of these selected rivers which are consumed by humans and livestock, as well as being used for irrigation system, and this constitutes a risk to public health. It also shows that A. baumannii and A. nosocomialis can thrive in the aquatic environment. This study suggests that direct utilization of water from these sources for domestic and other purposes without any form of pre-treatment should be avoided. It is, therefore, necessary for regulatory authorities to monitor the release of domestic and industrial wastewater into these water bodies in order to prevent outbreaks of epidemics. , Thesis (PhD) (Microbiology) -- University of Fort Hare, 2019
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Characterisation of human pathogenic vibrios and methicillin-resistant staphylococcus aureus (MRSA) from wild and tank cultured dusky kob (agyrosomus japonicus) in the Eastern Cape Province, South Africa
- Authors: Justine, Fri
- Date: 2017
- Subjects: Marine microbiology Marine microbiology--South Africa--Eastern Cape Staphylococcus aureus infections--South Africa--Eastern Cape
- Language: English
- Type: Thesis , Doctoral , Microbiology
- Identifier: http://hdl.handle.net/10353/16047 , vital:40607
- Description: Introduction: Marine finfish including dusky kob (Agyrosomus japonicus), in addition to its high protein value, is bestowed with numerous health benefits including being heart friendly due to high proportion of omega 3 fatty acids. They are therefore used as powerful preventive measures against cardiovaslcular diseases. They are also important in neurological development during gestation and infancy, thus a regular recommendation by nutritionists. However, fish and its environment may be contaminated by bacteria pathogens. Human infections caused by members of the genus Vibrio, and Staphylococcus especially Methicillin-resistant S. aureus (MRSA) are of increased concern worldwide especially with increased Vibrio disease outbreaks and rapid spread of MRSA in the community. Methicillin-resistant Staphylococcus aureus is regarded as an emerging zoonotic agent, therefore marine fish may be considered as a reservoir for infection. The emergence of multi-drug resistant organisms in both farm animals and humans has also been a challenge that hurdles chemotherapy worldwide. Methods: We enumerated the bacteria flora of skin, gill and gut of marine dusky kob (Agyrosomus japonicus) raised in a recirculatory aquaculture system using metagenomic sequencing of the 16S rRNA. We further screened 120 dusky kob fishes (skin, gill and gut) and 80 water samples from two fish farms and Kariega estuary collected over a 10 month period for human pathogenic vibrios, and MRSA using standard procedures. Vibrio species were further subjected to species specific PCRs delineating them into V. cholerae, V. parahaemolyticus, V. vulnificus, and V. fluvialis. This was followed by elucidation of the genotypic virulence determinants. The Reverse Fragment Length Polymorphism (RFLP) of the cytotoxin hemolysin (vvhA) gene of V. vulnificus strains was carried out to determine the associated biotypes. A total of 277 Vibrio strains consisting of 126 V. fluvialis, 45 Vibrio vulnificus, 30 V. parahaemolyticus and 76 vibrios belonging to other species were subjected to susceptibility testing to 15 antibiotics by the disc diffusion method and resistant strains were further evaluated for their genotypic antimicrobial resistant determinants by polymerase chain reaction followed by plasmid profiling. For MRSA screening, we evaluated the reliability of cefoxitin disc diffusion, oxacillin screen agar and BrillianceTM MRSA 2 agar tests, in detecting methicillin resistance from fish (environmental) samples using PCR detection of the mecA as the gold standard. A total of 33 mecA positive S. aureus strains (MRSA) were subjected to PCR detection of enterotoxins (Staphylococcal enterotoxin A-E) and Panton Valentine Leucocidin (PVL) encoding genes. The SCCmec types were also investigated by multiplex PCR targeting genes encoding type I-V. The antibiogram profiles of MRSA strains to 12 antibiotics by the disc diffusion method and to vancomycin by broth micro dilution method were elucidated. Polymerase chain reaction was employed to evaluate the presence of antibiotic resistant genes. The nucleotide sequences of the rpoB gene were analysed to determine mutations that could lead to rifampicin resistance. Results: A broad diversity of pathogenic and non-pathogenic bacterial species of different taxonomic groups was observed with Proteobacteria revealed as the most common bacteria phyla. Fifty one families were identified with Enterobacteriaceae the most frequently detected in all the anatomical sites and the gut showing the highest species diversity. A total of 606 (60.23 percent ) presumptive Vibrio isolates were confirmed by PCR of which V. fluvialis was the most predominant, 193 (31.85 percent ). This was followed by Vibrio vulnificus 74 (12.21 percent ), and V. parahaemolyticus 33 (5.45 percent ). No V. cholerae strain was detected. Only one of the V. parahaemolyticus strains possessed the trh virulent gene with no tdh detected. Virulence factors of V. fluvialis detected were stn (13.5 percent ), hupO (10.4 percent ), and vfpA (1.0 percent ). V. vulnificus biotype 3, formerly restricted to Isreal was identified. Generally, resistance among Vibrio isolates varied considerably with highest resistances recorded to amoxicillin (76.2 percent ), ampicillin (67.5 percent ), erythromycin (38.3 percent ), and doxycycline (35.0 percent ) while higher susceptibilities were revealed by gentamicin (100 percent ), norfloxacin (97.8 percent ), florfenicol (90.3 percent ), tetracycline (87.7 percent ), and chloramphenicol (87.4 percent ). Multiple antibiotic resistance (MAR) (resistance to ≥ 2 classes of antibiotics) was 58.5 percent . The MAR index did not vary significantly between sites (P>0.05) and values of >0.20 were recorded in 40 percent (108/277) of all the isolates. The resistant genes ampC, blaOXA, tetA, tetM, dfr1, sul1, sul2, ermB, nptII and strA were detected in two or more Vibrio isolates while the SXT intergrase was detected only in one isolate. Seven of the 18 extreme drug resistant isolates possessed 1–3 plasmids of 1.5–10 kb range. A total of 321 presumptive Staphylococcus aureus isolates were recovered by culture out of which 202 (62.9 percent ) were identified as S. aureus by PCR. Of these, 33 (16.3 percent ) strains were mecA positive while the rest, 169 (83.7 percent ) were mecA negative. The sensitivity and specificity of MRSA detection by use of cefoxitin disc (30 μg) test was 93.9 percent and 91.7 percent , that for oxacillin screen agar test (6 μg/mL) was 81.8 percent and 92.3 percent while that of BrillianceTM MRSATM 2 agar was 87.9 percent and 94.1 percent respectively. Staphylococcal enterotoxin SEE was detected in 12.1 percent (4/33) of total strains followed by SEA 3.0 percent (1/33), and SEC 3.0 percent (1/33). SEB and SED were absent. Six of the isolates had the PVL gene, giving a prevalence of 18.2 percent . The most frequently detected SCCmec type was SCCmec type III (17/33; 51.5 percent ), closely followed by SCCmec subtype IVc (10/33; 30.3 percent ) and the least were SCCmec types I and II with only 3.0 percent (1/33) each. The rest four (4/33; 12.1 percent ) did not belong to any of the above types and were therefore considered to belong to other subtypes of SCCmec type IV not tested in the study. For antibiogram patterns, 12 (36.4 percent ) strains were resistant to doxycyline, 10 (30.3 percent ) to trimethroprim-sulfamethoxazole, 9 (27.3 percent ) to tetracycline and only 1 (3.0 percent ) strain was resistant to ciprofloxacin. Nineteen (57.6 percent ) of the MRSA strains had vancomycin MIC of ≤ 2 μg/mL, 4 (12.1 percent ) with MIC range of 4-8 μg/mL, and 10 (30.3 percent ) with values ≥ 16 μg/mL. Overall, 27 (91.percent) isolates showed simultaneous resistance to 3 or more antibiotics. The resistant genes tetM, tetA, ermB, BlaZ femA were detected in two or more strains resistant to various antimicrobials. Resistance to rifampicin was not caused by mutations in the rpoB gene. Conclusions: To the best of our knowledge, this study is the first study reporting a broad, and diverse bacteria flora of skin, gill, and gut of the South African dusky kob as well as the first study on human pathogenic vibrios, and MRSA from marine finfish especially those from recirculatory aquaculture systems. Also, our study revealed that Vibrio species with pathogenic potential are present in marine dusky kob and its environs. Dusky kob is contaminated with CA- MRSA and HA- MRSA that may cause difficult to treat infections with regular antibiotics. Some of the MRSA strains contained toxins that can cause food-borne gastroeneteritis. The present study revealed that MRSA and Vibrio species are potential reservoirs for antibiotic resistant genes, which could be disseminated to other bacterial species probably through plasmids, a public health risk.
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Synthesis, characterization & comparative evaluation of photo-catalytic & antimicrobial activity of Ag2O and TiO2 immobilized on nanofibres for treatment
- Authors: Gxumisa, Xoliswa
- Date: 2014
- Subjects: Pollution http://id.loc.gov/authorities/subjects/sh85104530 , Titanium dioxide http://id.loc.gov/authorities/subjects/sh85135627 , Photocatalysis http://id.loc.gov/authorities/subjects/sh93001301
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10353/19545 , vital:43138
- Description: Water is a very essential substance for the existence of organisms and the environment where it functions as a transport medium for valuable chemicals, minerals, nutrients and also as a reaction medium. However, the remarkable water properties are not just limited to the dissolution of biological valuable substances, but also to harmful entities during pollution. This has led to research in the improvement and development of new techniques for water treatment. In this study, titanium dioxide (TiO2) and silver oxide (Ag2O) were prepared using the sol gel process and precipitation method respectively. The TiO2 was doped using a sol gel process with carbon and nitrogen so as to reduce the band gap. TiO2/Ag2O, N-TiO2/Ag2O and C-TiO2/Ag2O composites were also prepared using a precipitation method. The average particle size of prepared TiO2, C-TiO2, N-TiO2, Ag2O, TiO2/Ag2O, N-TiO2/Ag2O and CTiO2/Ag2O was found to be 13nm, 7nm, 10nm, 23nm, 28nm, 24nm and 21nm respectively as measured by TEM analysis. The photo-catalysts, Ag2O and TiO2 and their composites were immobilized on stabilized nanofibres using the electrospinning process to allow subsequent separation and reconciliation of the photo-catalyst after use in water treatment. The photocatalytic and antimicrobial activities of photo-catalysts were also evaluated using water contaminated with phenol red dye and Escherichia coli. The prepared materials were characterized by XRD, TEM, HRSEM, DRS, EDX, FT-IR, and TGA. Carbon was found to be more effective as a dopant than nitrogen. It reduced the band gap by 0.4 while nitrogen doping showed a reduction in band gap of 0.2 compared to undoped titanium dioxide. The doped TiO2 exhibited higher photo-catalytic and antimicrobial activity than the undoped TiO2. Introduction of Ag2O allowed utilization of visible light by the TiO2- Ag2O nano-composite leading to an improved rate of photo-degradation of phenol red and inactivation of E coli. Photo-catalytic properties showed that carbon doped materials have a higher photo-catalytic activity than nitrogen doped materials, while for antimicrobial v properties it is vice-versa. The immobilization of photo-catalysts on support material made it less effective towards the degradation of phenol red. The rate of photo-oxidation of phenol red was three times faster using powder TiO2 compared to immobilized TiO2. Therefore, this study suggests that photo-catalysis can be used as an effective method for water disinfection and production of potable and pathogen free drinking water even though better methods of immobilization should be sought. , Thesis (MSc) (Chemistry) -- University of Fort Hare, 2014
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Evaluation of flocculating potentials and charecterization of bioflocculants produced by three bacterial isolates from Algoa Bay, South Africa
- Authors: Okaiyeto, Kunle
- Date: 2016
- Subjects: Flocculation Water -- Purification -- Flocculation Water quality management
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/2633 , vital:27947
- Description: Flocculation has been widely adopted as one of the most effective methods to remove colloidal particles in water or wastewater treatment. Synthetic flocculants are conventionally used because of their high flocculating efficiency and cost-effectiveness. However, they have been reported to have hazardous properties and implicated in some serious health problems including senile dementia and neuro-toxicity, as well as being recalcitrant in the environment. Consequently, efforts are being geared away from the use of synthetic flocculants in water and wastewater treatment. Hence, the need for safe and eco-friendly flocculants has become imperative. Compared with synthetic flocculants, bioflocculants have special advantages such as safety, biodegradability and harmlessness to the environment and humans; attributes which make them potential alternatives in water treatment, downstream as well as fermentation processes. In the current study, the potentials of bacterial isolates recovered from Algoa Bay in the Eastern Cape Province of South Africa for bioflocculant production were investigated. The bacterial isolates were identified by polymerase chain reaction (PCR) as belonging to the Bacillus genus. The analysis of 16S ribosomal deoxyribonucleic acid (rDNA) nucleotide sequence of isolate M72 showed 99 percent similarity to Bacillus toyonensis strain BCT-7112 and was deposited in the GenBank as Bacillus toyonensis strain AEMREG6 with accession number KP406731. Likewise, the 16S rDNA nucleotide sequences of isolates M69 and M67 showed 98 percent sequence similarity to Bacillus licheniformis strain W7 and Bacillus algicola strain QD43 respectively; and M67 isolate was subsequently deposited in the GenBank as Bacillus sp. AEMREG7 with accession number KF933697.1. The results of the nutritional requirements and fermentation conditions revealed that optimum inoculum size for REG-6 production was 4 percent (v/v), while 5 percent (v/v) and 3 percent (v/v) were most favourable for MBF-W7 and MBF-UFH production respectively. Glucose was the best carbon source for the production of bioflocculants (REG-6 and MBF-UFH) by Bacillus toyonensis AEMREG6 and Bacillus sp. AEMREG7 respectively, while maltose supported optimum bioflocculant (MBF-W7) production by Bacillus specie. Inorganic nitrogen (NH4NO3) was the favoured nitrogen source for both REG-6 and MBF-W7 production, while mixed nitrogen sources [yeast extract + urea + (NH4)2SO4] supported the maximum production of MBF-UFH. The initial medium pH for REG-6 was 5, while MBF-W7 and MBF-UFH were both maximally produced at the initial pH of 6. After a 96 h cultivation period under optimal culture conditions, 3.2 g of purified REG-6 with a maximum flocculating activity of 77 percent was recovered from 1 L fermented broth of Bacillus toyonensis AEMREG6. Yields of 3.8 g and 1.6 g pure bioflocculants with the respective highest flocculating activities of 94.9 percent and 83.2 percent were also obtained from 1 L, 72 h-fermented broths of Bacillus licheniformis and Bacillus sp. AEMREG7 respectively. Furthermore, all the three bioflocculants (REG-6, MBF-W7 and MBF-UFH), displayed thermal stability within the temperature range of 50 to 100 oC, with strong flocculating activities of over 80 percent against kaolin suspension over a wide range of pH range (3–11) and relatively low dosage requirements of 0.1-03 mg/ml in the presence of divalent cations in the treatment of kaolin clay suspension and Thyme River waters. Chemical composition analyses of the bioflocculants showed them to be glycoproteins with a predominantly polysaccharide backbones as shown by the following carbohydrate/protein (w/w) ratios: 77.8 percent:11.5 percent (REG-6); 73.7 percent:6.2 percent (MBF-W7) and 76 percent:14 percent (MBF-UFH).
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Assessment of bioflocculant production by some marine bacteria isolated from the bottom sediment of Algoa Bay
- Authors: Cosa, Sekelwa
- Date: 2010
- Subjects: Flocculants , Bacteria -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Masters , MSc (Microbiology)
- Identifier: vital:11244 , http://hdl.handle.net/10353/404 , Flocculants , Bacteria -- South Africa -- Algoa Bay
- Description: Several problems concerning the use of conventional synthetic flocculants has necessitated the need for alternative cost effective, safe and efficient bioflocculants from microorganisms inhabiting many environments, particularly those from unusual environments. Hence, this study assessed bioflocculant production by three marine bacteria isolated from the bottom sediment of Algoa Bay in the Eastern Cape Province of South Africa. Analysis of the 16S rDNA sequences led to their identification as Halobacillus sp. Mvuyo, Virgibacillus sp. Rob and Oceanobacillus sp. Pinky. Several factors affecting the production and activity of the bioflocculant(s) were studied. Halobacillus sp. Mvuyo produced bioflocculant optimally with glucose (76%) and ammonium chloride (93%) as sole carbon and nitrogen sources, respectively and at neutral pH and in the presence of Ca2+. On the other hand, Virgibacillus sp. Rob preferred glucose (70.4 %) and iron sulphate (74%) as carbon and nitrogen source respectively; an alkaline pH (12.0) and Fe2+. Oceanobacillus sp. Pinky produced bioflocculant optimally when sucrose (80%) and peptone (72.4 %) were used as carbon and nitrogen source respectively, at neutral pH, and in the presence of Ca2+ cation. The chemical analyses of the partially purified bioflocculants revealed that the bioflocculants produced by Halobacillus sp. Mvuyo and Oceanobacillus sp. Pinky were glycoproteins, while that produced by Virgibacillus sp. Rob was a polysaccharide. We thus conclude that Halobacillus sp. Mvuyo, Virgibacillus sp. Rob and Oceanobacillus sp. Pinky hold promise as producers of new and efficient bioflocculant(s). We recommended development of process conditions for large scale production of the bioflocculants followed by their detailed characterization, as well as pilot scale assessment of the applicability of the purified bioflocculant in water/wastewater treatment and other industrial uses
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Assessment of bioflocculant production by two marine bacteria isolated from the bottom sediment of marine Algoa Bay
- Authors: Ntozonke, Ncedo
- Date: 2015
- Language: English
- Type: Thesis , Masters , MSc (Microbiology)
- Identifier: vital:11298 , http://hdl.handle.net/10353/d1021290
- Description: Bioflocculants are polymers, mostly, of microbial origin which floc out suspended particles from liquid medium. The ability of these biopolymers to remove suspended particles from solutions is termed bioflocculation, and the efficiency of flocculation activities depends on the characteristics of the flocculants. In comparison with conventionally used flocculants, bioflocculants have the advantage of being safe (no toxic effects known), biodegradable and harmlessness to the environment. The study assessed production of bioflocculant by two marine bacteria from the bottom sediment of marine environment. The 16S rDNA was used for identification, and the two bacteria species were identified as Enterococcus hirae and Bacillus thuringiensis. Factors affecting the production and activity of the bioflocculants produced by these two organisms were studied. The bacteria optimally produced bioflocculant with fructose (91.7%) and urea (91%) as sole carbon and nitrogen sources respectively. Mg2+ (87%) and Ca2+ (86%), likewise, served as best cation sources on the production of the bioflocculant at pH 5(93%). Additionally, the flocculating activity of the bioflocculant increased with the addition of Mg2+ (81%) and Na+ (81%), and the highest flocculating activity was at pH 5 of the kaolin clay. The Fourier transform infrared spectroscopy (FTIR) shows that the bioflocculant is a glycoprotein. The second bacterium (Bacillus thuringiensis) produced bioflocculant optimally when the media had mixed nitrogen sources (Urea, ammonium chloride and tryptone (67%)) and glucose (85.65%) as a sole carbon source, also Ca2+ (74.6%) was the best cation that induced the production of bioflocculant. After purification, the bioflocculant flocculated optimally in alkaline pH 12 (81%) in the presence of Mn2+ (73%) and Ca2+ (72.8%). Chemical analysis of the bioflocculant revealed it to be a polysaccharide. Both bioflocculants flocculate efficiently and can be used to replace synthetic flocculants in water treatment, wastewater, in downstream processing, and processing of food and chemicals and other industrial uses of flocculants. Challenges though (i) are to develop conditions for large scale production of the bioflocculant, (ii) to do further characterization of the both bioflocculants (iii) to assess the bioflocculants for treatments of water/wastewater, and to apply it in various industrial processes.
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Performance of magnetic nanocomposites for the removal of some selected contaminants from aqueous solution
- Authors: Ojemaye, Mike Onyewelehi
- Date: 2017
- Subjects: Nanocomposites (Materials)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10353/8746 , vital:33508
- Description: In this thesis, the performances of magnetic nanoparticles based materials were assessed for the removal or reduction of heavy metals in aqueous solutions. The successful synthesis of a novel adsorbent, azomethine functionalized magnetic nanoparticles (MNP-Maph) by covalent bonding between the amine group (-NH2) of amine functionalized magnetic nanoparticles (MNP-NH2) and carboxylic group (-COOH) of 4-{[(E)-phenylmethylidene]amino}benzoic acid (Maph-COOH) was achieved. This adsorbent was examined for the removal of di and trivalent ions (Cu2+, Zn2+, As3+, Pb2+ and Hg2+) from aqueous solutions. Also, magnetic photocatalyst with silica interlayer (NiFe2O4-SiO2-TiO2) was synthesized and employed for the reduction of Cr(VI) in aqueous solution. The photocatalytic reduction efficiency of this material was compared with that of magnetic titanium dioxide (NiFe2O4-TiO2) photocatalyst and titanium dioxide (TiO2) to ascertain the material with the best photocatalytic efficiency and ease of separation. All synthesized materials were characterized by using XRD, FT-IR, TEM, SEM, TGA and VSM before application. For the adsorption processes, the effects of pH, contact time, adsorbent dose and temperature were examined to ascertain the experimental condition necessary for the optimal removal of metal ions from solution. The data obtained from all experiments were fitted into four kinetic models; pseudo-first order, pseudo-second order, elovich and intra particle diffusion models to determine the mechanism involved in the adsorption of these di and trivalent ions while two isotherm models were employed in the adorption processes; these include: Langmuir and Freudlich models. Also, for the photocatalytic experiment, the effects of pH, contact time and photocatalyst dose were investigated to determine the experimental conditions necessary for the optimal reduction of Cr(VI) in aqueous solution. MNP-Maph showed excellent removal capacities of 34.08, 35.83, 50.08, 58.24 and 59.24 mg g-1 for Cu2+, Zn2+, As3+, Pb2+ and Hg2+ respectively compared to data previously reported in literature. This is as a result of the high affinity of azomethine group towards metal ions which tremendously enhanced removal of metal ions by adsorption. The incorporation of azomethine to magnetic nanoparticles improved the affinity towards metal ions removal forming strong electrostatic interaction between the adsorbent active sites and adsorbates. Also, the utilization of NiFe2O4-SiO2-TiO4, NiFe2O4-TiO2 and TiO2 for the reduction of Cr(VI) in aqueous solution showed a good photocatalytic performance with NiFe2O4-SiO2-TiO2 showing to be better in terms of both photocatalytic reduction and magnetic separation. TiO2 was observed to have 96.7percent reduction efficiency within 240 min while NiFe2O4-SiO2-TiO2 has 96.5percent reduction efficiency within 300 min and NiFe2O4-TiO2 gave 60percent reduction efficiency within 300 min of UV irradiation. This magnetic photocatalyst composite (NiFe2O4-SiO2-TiO2) gives the advantage of avoiding the problem of separation often encountered with most photocatalyst materials including TiO2 by allowing separation with the aid of a magnetic field. The adsorption processes were all described by pseudo-second order and Langmuir isotherm models while the photocatalytic process was described by Langmuir-Hinshelwood (L-H) kinetic model. Furthermore, thermodynamic experiment studied for the adsorption processes showed that all metal ion adsorption except Hg2+ by MNP-Maph were endothermic in nature, rapid and spontaneous indicating the feasibility of the sorbent material for the removal of metal ions from aqueous solutions. Also, regenerability study conducted to determine the reusability of sorbent material after seven cycles showed the potential to reuse sorbent material seven times or more. The reusability of the sorbent material was observed to show a percentage of an average of 78percent using 50:50 mixture of 0.1 mol dm-3 HNO3 and HCl for all adsorption processes. For the photocatalytic experiment, regenerability using 0.1 mol dm-3 for 1 h was observed to be very impressive after 3 runs for all synthesized photocatalytic materials. This thereby implies that the removal of metal ions by these materials will not in any way introduce secondary pollutants into the environment. Rather, it will avert the production of secondary pollutants. Also, the use of simple conventional chemicals for the regeneration of synthesized materials showed that regeneration in this study is cost effective as regeneration has been known to cost about three quarter of the total operation and maintenance of an adsorption or photocatalytic process. Application of MNP-Maph to real wastewater sampled from five different wastewater treatment plants in Eastern Cape Province for the removal of Cu2+, Zn2+ and As3+ showed that removal efficiencies of approximately 80 percent were achieved for all three metal ions upon adsorption by MNP-Maph. These therefore show that the introduction of metal loving ligand such as Maph-COOH improved the efficiency of MNP towards the removal of heavy metal ions from aqueous solution. Also, silica positively influenced the performance of magnetic titanium dioxide towards Cr(VI) reduction and separation from aqueous solution. This study therefore showed that these materials should be considered for future applications in the area of water/wastewater decontamination.
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Synthesis and characterization of metal sulfide nanoparticles/polymer nanocomposites
- Authors: Mbese, Johannes Zanoxolo
- Date: 2013
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11344 , http://hdl.handle.net/10353/d1016190
- Description: The focus of this project was to synthesize and characterize metal sulfide nanoparticles /polymer nanocomposites. The work involved the synthesis of dithiocarbamato ligands and complexes derived from aniline. Zn(II), Cd(II) and Hg(II) dithiocarbamato complexes were used as single-molecule precursors for the synthesis of the ZnS, CdS and HgS nanoparticles and their optical and structural properties studied. The other focus of this work was to synthesize a combined functionality metal sulfide nanoparticles/polymer nanocomposites by dispersing as-synthesized ZnS, CdS and HgS nanoparticles in polymethyl methacrylate (PMMA) matrix. The characterization of the ligands, complexes, nanoparticles and nanocomposites were investigated using relevant instrumental tools like UV-Vis, photoluminescence (PL), Fourier transform infrared (FTIR), X-ray diffraction (XRD), energy dispersion X-ray (EDX), nuclear magnetic resonance (NMR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM).
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Diet of the yellow mongoose (Cynictis penicillata) in the Albany Thicket Biome of South Africa
- Authors: Bizani, Mfundo
- Date: 2014
- Language: English
- Type: Thesis , Masters , MSc (Zoology)
- Identifier: vital:11796 , http://hdl.handle.net/10353/d1019840
- Description: The dietary habits of the yellow mongoose Cynictis penicillata were studied in the Albany Thicket Biome of South Africa (Great Fish River Reserve, Eastern Cape). The diet was investigated through the analysis of 1,056 scats that were sampled over a period of 7 years (2005−2009 and 2011−2012) mainly in three similar sites (Kelarny, Grasslands and Junction 10) that were used by at least three families or groups of yellow mongooses. Scats were collected near latrine sites, labelled and stored in a freezer. In the laboratory, scats were oven dried for a period of 24 hours at 50 C. Diet was determined by identifying undigested food remains in the scats. Hair samples were examined under the compound microscope to identify which mammals were ingested. In the field, both arthropod and small mammal abundance were determined in order to evaluate whether yellow mongooses are opportunistic or specialist feeders. Furthermore, inter-annual (2006–2008) and inter-group/inter-site variations in the diet were assessed. Based on faecal analysis, arthropods were the principal prey, while small mammals acted as supplementary food item. Other food categories like vegetation, reptiles and birds were only ingested or preyed upon infrequently. Intermediate dietary diversity, and low standardised diet breadth indices were obtained for all seasons, as well as for the whole sampling period. The diet overlaps calculated for pairs of seasons were very high and did not differ substantially. However, the diet of the yellow mongoose varied seasonally, yearly and between groups (sites), mostly due to variations in arthropod and small mammal consumption. Food availability displayed an increase in biomass of both small mammals and arthropods in summer and autumn. Results obtained in this study could suggest that the yellow mongoose at the GFRR is insectivorous by preferring to feed on insects (and arthropods in general) when both insects and rodents are abundant. However the fact that its diet varies both seasonally, yearly and locally, as well as the presence of remains of other food categories in the scats, indicates that this species is rather an opportunistic, generalist feeder than an insect specialist.
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Synthesis and characterization of titanium dioxide nanotubes on fluorine-doped tin oxide (FTO) glass substrate using electro-anodization technique
- Authors: Zinya, Simcelile https://orcid.org/0000-0001-5864-0957
- Date: 2017-12
- Subjects: Titanium dioxide , Nanotubes , Nanostructured materials
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10353/23979 , vital:62201
- Description: One-dimensional (1-D) titanium dioxide nanotubes (TNTs) have attracted much attention as a promising alternative electrode material for dye sensitized solar cell (DSSC). As compared to the randomly packed and disordered TiO2 nanoparticles (TNPs) network with numerous particle-particle interfaces, TNTs prove to have fascinating features than make them suitable candidates in DSSCs. Well-structured TNTs arrays are of great potential among the various types of 1D TiO2 nano-materials owing to their superior electron transport properties with limited grain boundaries. Vectorial transport of photon generated electrons along the TNTs has been reported to lead to higher charge mobility which is crucial for improvement of DSSC performances. In this work, highly adhesive titanium films were deposited on functional substrates (FS) using radio frequency (RF) sputtering technique at a sputtering output power of 1kW, operating pressure of 1.5 Pa and at a deposition temperature of 200 °C to obtain a thickness of 10 μm under an inert argon atmosphere. The duration period for sputter coating 10 μm thickness of titanium film layer was 122 minutes with sputter rate for titanium target of about 82 nm per minutes. Subsequently, the RF sputtered titanium films were anodized with 0.5 wt. percent ammonium fluoride + 0.35 wt. percent deionised water and 96 wt. percent glycerol electrolyte solution at room temperature at 60 V for 72 hours. The resulting TNTs on functional substrates (TNTs-FS) were subjected to thermal treatment at 350 °C, 450 °C, 550 °C and 650 °C for 3 hours under oxygen atmosphere. The effect of annealing temperature on the morphological, and structural properties have been scrutinized. The as prepared and thermally treated TNTs-FS were characterized using scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and Confocal Raman Spectroscopy (CRS). SEM and HRTEM techniques were employed to confirm the presence of the TNTs-FS and also to study the structural-morphology of the TNTs as the annealing temperature increases. SEM revealed improvement in morphology with increase in sample annealing temperature, even at high temperatures such as 650 °C with no collapsing and sintering of the TNTs-FS occurring. SEM images revealed TNTs-FS with pore diameter sizes in the range between 85-170 nm. This is in compliance with HRTEM analysis, which revealed smooth and straight tube walls and improved surface morphology with increase in annealing temperature. In addition HRTEM images revealed pore diameter of TNTs-FS in the range between 85-165 nm. Furthermore, HRTEM revealed lattice fringes of 0.351, 0.352 and 0.353 nm between the neighbouring lattice fringes. All corresponding to (101) planes of anatase phase TNTs at different annealing temperatures (350-650 °C). The crystallographic structure of TNTs-FS was characterized by XRD measurements after thermal treatment at 350 °C, 450 °C, 550 °C and 650 °C. The XRD pattern revealed peaks in the wide angle range of 2θ (20° < 2θ > 80°) discovered at 29.43°, 45.10°, 56.52°, 63.5°, 64.92° and 74.81° corresponding to the planes (101), (112), (200), (105), (211) and (204) crystalline structures of the anatase TNTs. The intensity of the peaks increased with increasing annealing temperature. The strong sharp peaks indicate the large quantities and higher degrees of crystallinity of anatase phase of the TNTs. CRS Large Area Scan (LAS) and Depth profiling (DP) were employed to evaluate the crystallinity and phase distribution of TNTs-FS thermally treated at different temperatures. CRS LAS in the XY direction of TNTs-FS revealed the presence of differently crystallized anatase phases of TiO2 with Raman vibrational modes of 159.38 cm-1 (Eg), 208.37 cm-1 (Eg), 399.67 cm-1 (B1g), 514.25 cm-1 (A1g) and 641.58 cm-1 (Eg) for the samples annealed at 350 °C. The effect of annealing temperature on TiO2 phase evolution was meticulously evaluated using CRS for TNTs-FS for the samples annealed at 350 °C, 450 °C, 550 °C and 650 °C. The FWHM was estimated from CRS and decreases with increasing annealing temperature resulting in increasing crystallinity. Increase in anatase FWHM and anatase peak intensity implies higher degree of crystallinity and increasing crystallite sizes were also confirmed by XRD. Growing of titanium dioxide on functional substrates one novel contribution towards the fabrication of efficient electrode materials for solar cell development. Our method of characterizing TNTs-FS from a large area scan along the surface of the samples and depth profiling along the TNTs tube walls using confocal Raman spectroscopy prove to be a pivotal step in the development of efficient photoelectrode materials of the solar devices. , Thesis (MSc) -- Faculty of Science and Agriculture, 2017
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Evaluation of functionalized silver and silica nanoparticles for the removal of deoxyribonucleic acid conveying antibiotics resistance genes from water
- Authors: Ezeuko, Adaora Stella
- Date: 2022
- Subjects: DNA , Silica , Water
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10353/27765 , vital:69414
- Description: Antibiotic resistance genes ARGs are recognized as a serious public health emergency linked to extensive use of antibiotics by humans and animals as a prophylactic agent that treats and prevents infections. The occurrence of high concentrations being identified in wastewater treatment plants, rivers, etc is due to untreated effluents being discharged from households, hospitals, agriculture, and pharmaceutical industries. The application of adequate treatment techniques and material for the removal of bacteria DNA conveying ARGs from the effluents before their release to the environment cannot be overemphasized. Adsorption techniques seem to be effective due to their easy design, operation, and ability to regenerate adsorbents for use without producing toxic by-products. This concept was employed for the removal of bacteria DNA conveying ARGs from simulated aqueous solution, effluents from hospital, river and WWTPs using silver and silica metallic nanoparticles. This thesis investigated the effectiveness of metallic nanoparticles containing silver AgNPs and mesoporous silica nanoparticles MSNPs as well as magnetite Fe3O4 functionalized with 4 4hydroxyphenyl 2 262-terpyridine onto their surface, for the removal of bacteria DNA conveying antibiotic resistance genes from water samples from hospitals, river, and wastewater treatment plants WWTPs. Silver nanoparticles AgNPs of different molar concentrations 0.1M, 0.5M and 1.0 M and mesoporous silica nanoparticles MSNPs adsorbents were successfully synthesized in their original states and surface functionalization achieved by incorporating magnetite Fe3O4 and 4 4 hydroxyphenyl 2 2 6 2 terpyridine on the silver AgNPs Fe3O4 and silica MSNPs TPPY surfaces respectively. Their effectiveness as adsorbent for the removal of bacteria DNA conveying ARGs from aqueous solutions and real water/wastewater samples were investigated. The DNA uptake by the as-synthesized AgNPs and MSNPs were compared to the functionalized AgNPs Fe3O4 and MSNPsTPPY by determining the adsorbents with the highest removal efficiencies. All as synthesized and functionalized adsorbents were characterized by SEM, EDX, FTIR, XRD, UV spectroscopy and PZC before the removal process. The extraction of genomic DNA from antibiotic-resistant Enterococcus faecium and Vibrio parahaemolyticus was successfully achieved via the boiling method. Antibiotic susceptibility test was conducted using the disk diffusion method before the commencement of genomic DNA extraction. Molecular characterization via gel electrophoresis confirmed the presence of resistance genes at different base pairs. Adsorption batch experiment were investigated, and the best optimum parameters were evaluated through the influence of pH, contact time, initial DNA concentration, adsorbent dose, and competitive ions for each sorption process. The rate determining step were determined by fitting kinetic models such as Natarajan and Khalaf first order, pseudo first order, pseudo second order, Elovich model to experimental data. Also, the adsorption mechanisms determining adsorption equilibrium were investigated by fitting Freundlich, Langmuir and Sips model into the experimental data. The application of AgNPsFe3O4 nanocomposite and MSNPsTPPY for the removal of bacteria DNA demonstrated much enhancement for DNA uptake than the as-synthesized AgNPs and MSNPs materials. The incorporation of magnetite and 4 4hydroxyphenyl 2 2 6 2-terpyridine onto AgNPs and MSNPs significantly enhanced the binding affinity towards the removal the bacteria DNA via strong electrostatic attraction between the active sites on the adsorbent and the negative DNA molecules. Finally, high adsorption capacities were recorded with AgNPsFe3O4 nanocomposite and MSNPsTPPY compared to AgNPs and MSNPs with chaotropic salts. The kinetic adsorption models were mostly best fitted by the pseudo-second order and Elovich models while the adsorption equilibrium was best described by Langmuir and Sips isotherm models. MSNPs with different chaotropic salts, AgNPsFe3O4 nanocomposite and MSNPsTPPY also proved its effectiveness in DNA removal not only in the simulated aqueous solution but in three different real life water samples obtained from Cofimvaba hospital, Ndevana river and Uitenhage WWTPs. High adsorption efficiencies above 90 percent were achieved during the removal of DNA in all the three real water samples. Therefore, application of these adsorbents for the removal of bacteria DNA conveying ARGs may be a promising option that would tackle the consequences of consuming ARGs infected water globally. , Thesis (MSc) -- Faculty of Science and Agriculture, 2022
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Synthesis and application of coal fly ash supported C doped TiO2/SnO2 photocatalyst in water treatment
- Authors: Sambakanya, Siyasanga
- Date: 2020
- Subjects: Photocatalysis
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: http://hdl.handle.net/10353/18838 , vital:42869
- Description: Coal fly ash supported carbon doped titanium dioxide/tin oxide (C doped TiO2-SnO2/CFA) nanoparticles were successfully synthesised using a sol gel method and calcined at 550 °C. The crystal structure, optical properties, morphology and other properties were analysed using XRD, UV-Vis, FTIR, TEM, SEM, DRS and EDX. SEM analysis showed that the nanoparticles (NPs) of C doped TiO2-SnO2/CFA were quasi spherical. XRD showed that C doped TiO2-SnO2/CFA nanoparticles were polycrystalline and consisted of both rutile and anatase phases. TEM analysis also displayed small NPs of C-TiO2-SnO2/CFA (12.62 nm) than TiO2 (16.19 nm) and SnO2 (19.98 nm). DRS revealed reduced band gap of C-TiO2 (2.78 eV) than TiO2 (3.19 eV) after doping. The photocatalytic efficiency of the prepared C-TiO2-SnO2/CFA nanoparticles was determined using methyl orange (MO) and methylene blue dye (MB) as standard dyes in the photodegradation as well as lead and mercury in the photoreduction of lead and mercury ions in water. The degradation experiments were carried under natural solar irradiation and UV light. The photodegradation experiments carried under visible light showed excellent photodegradation of MO & MB in water. This is a good indication that doping was successful as it imparted visible light activity in the C-TiO2-SnO2/CFA NPs. The photocatalyst efficiency was further tested while varying parameters including photocatalyst load, pH, and initial pollutant concentration in the photodegradation of MO & MB as well as in photoreduction of Pb2+ and Hg2+ in water to establish optimum operating conditions. The degradation rate of MO & MB increased when photocatalyst loading increased. When the pH was increased, the photocatalytic efficiency of the prepared photocatalyst towards methyl orange was reduced; however methylene blue degradation increased with increase in pH. The reduction of Pb2+ also increased with increasing pH whereas that of Hg2+ increased with decreasing pH. It was found that photodegradation was directly proportional to and photoreduction was inversely proportional to initial pollutant concentration.
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