Research Outputs (Chemistry)
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Item Attenuation of pollution arising from acid mine drainage by a natural wetland on the Witwatersrand(Academy of Science of South Africa (ASSAf), 2017-01) Humphries, M.S.; McCarthy, T.S.; Pillay, L.Wetlands are well known to be efficient at sequestering pollutants from contaminated water. We investigated metal accumulation in the peats of the Klip River, a natural wetland that has received contaminated water from gold mining operations in Johannesburg for over 130 years. Previous work conducted in the downstream portion identified the wetland as an important system for sequestering metals. We focused on the upstream section of the wetland, more proximal to the source of acid mine drainage, to provide a better understanding of the pollutant sources and the role of the wetland in pollutant attenuation. Geochemical and mineralogical analyses of peat cores revealed considerable metal enrichments in the peat ash, particularly in Co, Ni, Zn, Pb, Cu and U. Metal concentrations are typically between 4 to 8 times higher than those previously reported for the downstream, more distal portion of the wetland. The distribution of metal accumulation within the peat profiles suggests that contamination arises from a combination of sources and processes. Elevated concentrations in the shallow peat are attributed to the input of contaminated surface water via tributaries that drain the Central Rand Goldfield, whereas enrichments in the deeper peat suggest significant sub-surface inflow of contaminated water through the underlying dolomitic rocks. Metal immobilisation occurs through a combination of mechanisms, which include the precipitation of gypsum, metal sulfides, Fe-Mn oxyhydroxides and phosphates. Our study highlights the environmental and economic importance of natural wetland systems which have the ability to accumulate large quantities of metals and thus remediate polluted waters.Item Hierarchical one-dimensional ammonium nickel phosphate microrods for high-performance pseudocapacitors(Nature Publishing Group, 2015-12) Raju, K.; Ozoemena, K.I.High-performance electrochemical capacitors will drive the next-generation portable, flexible and wearable electronics. Unlike the conventional all-carbon supercapacitors (electric double layer capacitors, EDLC) with high power but poor energy density, pseudocapacitors capitalize the high energy density inherent to reversible redox reactions and provide a facile means to enhancing the energy ratings of supercapacitors. The high length-to-diameter ratio and anisotropic character of 1-D architecture makes them suitable for use in energy storage. For the first time, we report 1-D microrod structures (∼ 36 nm width) of ammonium nickel phosphate hydrate (ANP mr) as a pseudocapacitor with high energy rating and power handling. To confirm the data, the ANP mr -based pseudocapacitor was subjected to various configurations (i.e., half-cell, symmetric, asymmetric, and flexible all-solid-state) and in each case it gave excellent values compared to any accessible literature to date. We clearly demonstrate that a flexible all-solid-state ANP mr -based pseudocapacitor achieved high areal capacitance of 66 mF cm ∼'2 with extra-ordinary energy (21.2 mWh cm ∼'2) and power (12.7 mW cm ∼'2) densities. This work opens doors for a facile, robust and scalable preparation strategy for low-cost, earth-abundant electrode materials for high-performance pseudocapacitors.Item A structural study of 4-aminoantipyrine and six of its Schiff base derivatives(International Union of Crystallography, 2015-02) Mnguni, M.J.; Lemmerer, A.Six derivatives of 4-amino-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one (4-aminoantipyrine), C11H13N3O, (I), have been synthesized and structurally characterized to investigate the changes in the observed hydrogen-bonding motifs compared to the original 4-aminoantipyrine. The derivatives were synthesized from the reactions of 4-aminoantipyrine with various aldehyde-, ketone- and ester-containing molecules, producing (Z)-methyl 3-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]but-2-enoate, C16H19N3O3, (II), (Z)-ethyl 3-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]but-2-enoate, C17H21N3O3, (III), ethyl 2-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]cyclohex-1-enecarboxylate, C20H25N3O3, (IV), (Z)-ethyl 3-[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]-3-phenylacrylate, C22H23N3O3, (V), 2-cyano-N-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)acetamide, C14H14N4O2, (VI), and (E)-methyl 4-{[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]methyl}benzoate, C20H19N3O3, (VII). The asymmetric units of all these compounds have one molecule on a general position. The hydrogen bonding in (I) forms chains of molecules via intermolecular N-H⋯O hydrogen bonds around a crystallographic sixfold screw axis. In contrast, the formation of enamines for all derived compounds except (VII) favours the formation of a six-membered intramolecular N-H⋯O hydrogen-bonded ring in (II)-(V) and an intermolecular N-H⋯O hydrogen bond in (VI), whereas there is an intramolecular C-H⋯O hydrogen bond in the structure of imine (VII). All the reported compounds, except for (II), feature π-π interactions, while C-H⋯π interactions are observed in (II), C-H⋯O interactions are observed in (I), (III), (V) and (VI), and a C-O⋯π interaction is observed in (II).Item Crystal structures of 2,2′-bipyridin-1-ium 1,1,3,3-tetracyano-2-ethoxyprop-2-en-1-ide and bis(2,2′-bipyridin-1-ium) 1,1,3,3-tetracyano-2-(dicyano-methylene) propane-1,3-diide(International Union of Crystallography, 2015-05) Setifi, Z.; Valkonen, A.; Fernandes, M.A.; Glidewell, C.; Harrison, W.T.A.; Nummelin, S.; Boughzala, H.; Setifi, F.In 2,2′-bipyridin-1-ium 1,1,3,3-tetracyano-2-ethoxyprop-2-en-1-ide, C10H9N2+·-C9H5N4O-, (I), the ethyl group in the anion is disordered over two sets of atomic sites with occupancies 0.634 (9) and 0.366 (9), and the dihedral angle between the ring planes in the cation is 2.11 (7)°. The two independent C(CN)2 groups in the anion make dihedral angles of 10.60 (6) and 12.44 (4)° with the central propenide unit, and the bond distances in the anion provide evidence for extensive electronic delocalization. In bis(2,2′-bipyridin-1-ium) 1,1,3,3-tetra-cyano-2-(dicyanomethylene) propane-1,3-diide [alternative name bis(2,2′-bipyr-idin-1-ium) tris(dicyanomethylene) methanediide], 2C10H9N2+·C10N62- (II), the dihedral angles between the ring planes in the two independent cations are 7.7 (2) and 10.92 (17)°. The anion exhibits approximate C3 symmetry, consistent with extensive electronic delocalization, and the three independent C(CN)2 groups make dihedral angles of 23.8 (2), 27.0 (3) and 27.4 (2)° with the central plane. The ions in (I) are linked by an N - H⋯N hydrogen bond and the resulting ion pairs are linked by two independent C - H⋯N hydrogen bonds, forming a ribbon containing alternating R44(18) and R44(26) rings, where both ring types are centrosymmetric. The ions in (II) are linked by two independent N - H⋯N hydrogen bonds and the resulting ion triplets are linked by a C - H⋯N hydrogen bond, forming a C12(7) chain containing anions and only one type of cation, with the other cation linked to the chain by a further C - H⋯N hydrogen bond.Item The effect of structural properties of Cu2Se/polyvinylcarbazole nanocomposites on the performance of hybrid solar cells(Hindawi Publishing Corporation, 2016) Govindraju, S.; Ntholeng, N.; Ranganathan, K.; Sikhwivhilu, L.M.; Moloto, N.; Moloto, M.J.It has been said that substitution of fullerenes with semiconductor nanocrystals in bulk heterojunction solar cells can potentially increase the power conversion efficiencies (PCE) of these devices far beyond the 10% mark. However new semiconductor nanocrystals other than the potentially toxic CdSe and PbS are necessary. Herein we report on the synthesis of Cu2Se nanocrystals and their incorporation into polyvinylcarbazole (PVK) to form polymer nanocomposites for use as active layers in hybrid solar cells. Nearly monodispersed 4 nm Cu2Se nanocrystals were synthesized using the conventional colloidal synthesis. Varying weight % of these nanocrystals was added to PVK to form polymer nanocomposites. The 10% polymer nanocomposite showed retention of the properties of the pure polymer whilst the 50% resulted in a complete breakdown of the polymeric structure as evident from the FTIR, TGA, and SEM. The lack of transport channels in the 50% polymer nanocomposite solar cell resulted in a device with no photoresponse whilst the 10% polymer nanocomposite resulted in a device with an open circuit voltage of 0.50 V, a short circuit current of 7.34 mA/cm2, and a fill factor of 22.28% resulting in a PCE of 1.02%.Item The effect of temperature and methanol-water mixture on pressurized hot water extraction (PHWE) of anti-HIV analogoues from Bidens pilosa(BioMed Central Ltd., 2016-06) Gbashi, S.; Njobeh, P.; Steenkamp, P.; Tutu, H.; Madala, N.Background: Pressurized hot water extraction (PHWE) technique has recently gain much attention for the extraction of biologically active compounds from plant tissues for analytical purposes, due to the limited use of organic solvents, its cost-effectiveness, ease-of-use and efficiency. An increase in temperature results in higher yields, however, issues with degradation of some metabolites (e.g. tartrate esters) when PHWE is conditioned at elevated temperatures has greatly limited its use. In this study, we considered possibilities of optimizing PHWE of some specific functional metabolites from Bidens pilosa using solvent compositions of 0, 20, 40 and 60 % methanol and a temperature profile of 50, 100 and 150 °C. Results: The extracts obtained were analyzed using UPLC-qTOF-MS/MS and the results showed that both temperature and solvent composition were critical for efficient recovery of target metabolites, i.e., dicaffeoylquinic acid (diCQA) and chicoric acid (CA), which are known to possess anti-HIV properties. It was also possible to extract different isomers (possibly cis-geometrical isomers) of these molecules. Significantly differential (p ≤ 0.05) recovery patterns corresponding to the extraction conditions were observed as recovery increased with increase in methanol composition as well as temperature. The major compounds recovered in descending order were 3,5-diCQA with relative peak intensity of 204.23 ± 3.16 extracted at 50 °C and 60 % methanol; chicoric acid (141.00 ± 3.55) at 50 °C and 60 % methanol; 4,5-diCQA (108.05 ± 4.76) at 150 °C and 0 % methanol; 3,4-diCQA (53.04 ± 13.49) at 150 °C and 0 % methanol; chicoric acid isomer (40.01 ± 1.14) at 150 °C and 20 % methanol; and cis-3,5-diCQA (12.07 ± 5.54) at 100 °C and 60 % methanol. Fitting the central composite design response surface model to our data generated models that fit the data well with R2 values ranging from 0.57 to 0.87. Accordingly, it was possible to observe on the response surface plots the effects of temperature and solvent composition on the recovery patterns of these metabolites as well as to establish the optimum extraction conditions. Furthermore, the pareto charts revealed that methanol composition had a stronger effect on extraction yield than temperature. Conclusion: Using methanol as a co-solvent resulted in significantly higher (p ≤ 0.05) even at temperatures as low as 50 °C, thus undermining the limitation of thermal degradation at higher temperatures during PHWE.Item Removal of uranium from aqueous solutions using ammonium-modified zeolite(South African Chemical Institute, 2015) Bakatula, E.N.; Mosai, A.K.; Tutu, H.Batch experiments were conducted to study the effects of contact time, pH (3 to 8), initial concentration, presence of carbonate, sulphate, and competing ions (Fe3+, Ca2+, Sr2+, Mg2+) on the adsorption of U(VI) on ammonium-modified zeolite (AMZ). The structural features of the modified zeolite were assessed by Fourier Transform Infra Red Spectroscopy (FTIR) while the metal content was determined by Inductively Coupled Plasma Optical Emission Specroscopy (ICP-OES). The removal of uranium was effective and maximal under acidic conditions (pH 3 to 5). The kinetics of adsorption of U-nitrate and U-sulphate on AMZ were described by the pseudo-second-order model (R2 ≥ 0.9820). In the presence of SO4 2- and CO3 2-, a significant reduction of 67.88 % and 71.63 %, respectively, in uranium uptake was observed. The distribution coefficient, KD (L g-1), was in the order of: U-nitrate (1.116) > U-sulphate (0.029) > U-carbonate (0.019), suggesting that AMZ had a high affinity for U-nitrate. The presence of Fe3+ enhanced the removal of U(VI) from U-nitrate, U-sulphate and U-carbonate by 20.18 %, 72.48 % and 82.43 %, respectively, while the presence of Ca2+, Mg2+ and Sr2+ reduced the removal to 19.57 %, 31.60 % and 23.65 %, respectively. AMZ is an effective adsorbent for uranium removal from aqueous solutions dominated by nitrate, carbonate and sulphate.Item Selective adsorption of uranium (VI) on NaHCO3 leached composite γ-methacryloxypropyltrimethoxysilane coated magnetic ion-imprinted polymers prepared by precipitation polymerization(South African Chemical Institute, 2015) Tavengwa, N.T.; Cukrowska, E.; Chimuka, L.Ion imprinted nano-magnetic composite polymers for selective removal of hexavalent uranium were prepared by a precipitation polymerization technique in the presence of γ-methacryloxypropyltrimethoxysilane (γ-MPS) coated magnetite and other pre-polymerization reagents. The synthesized magnetic polymers were then leached with NaHCO3 to produce magnetic ion imprinted polymers (IIPs) with fabricated adsorption sites complementary to the uranyl ions in terms of size and shape. Several parameters were investigated to obtain conditions which gave the optimum adsorption of the uranyl onto the magnetic IIPs and their corresponding controls, magnetic ion non-imprinted polymers (NIPs). The optimum amount of magnetic sorbent, initial concentration and contact time were 50 mg, 2.5 mg L-1 and 45 min, respectively. The adsorption capacity of the magnetic IIP (1.15 ± 0.01 mg g-1) was higher than that of the magnetic NIP (0.93 ± 0.02 mg g-1). This indicated that the former had a somewhat higher affinity for U(VI) than the later. The magnetic polymers also displayed good selectivity of the order: U(VI) > Ni(II) > Mg(II). After six cycles of use, the magnetic polymers illustrated good stability and reusability.Item Passive remediation of acid mine drainage using cryptocrystalline magnesite: A batch experimental and geochemical modelling approach(South African Water Research Commission, 2015-10) Masindi, V.; Gitari, M.W.; Tutu, H.; De Beer, M.Acid mine drainage is generated when mining activities expose sulphidic rock to water and oxygen leading to generation of sulphuric acid effluents rich in Fe, Al, SO4 and Mn with minor concentrations of Zn, Cu, Mg, Ca, Pb depending on the geology of the rock hosting the minerals. These effluents must be collected and treated before release into surface water bodies. Mining companies are in constant search for cheaper, effective and efficient mine water treatment technologies. This study assessed the potential of applying magnesite as an initial remediation step in an integrated acid mine drainage (AMD) management system. Neutralization and metal attenuation was evaluated using batch laboratory experiments and simulations using geochemical modelling. Contact of AMD with cryptocrystalline magnesite for 60 min at 1 g: 100 mℓ S/L ratio led to an increase in pH, and a significant increase in metals attenuation. Sulphate concentration was reduced to ≈1 910 mg/ℓ. PH redox equilibrium (in C language) (PHREEQC) geochemical modelling results showed that metals precipitated out of solution to form complex mineral phases of oxy-hydroxysulphates, hydroxides, gypsum and dolomite. The results of this study showed that magnesite has potential to neutralize AMD, leading to the reduction of sulphate and precipitation of metals.Item Leachability of metals from gold tailings by rainwater: An experimental and geochemical modelling approach.(South African Water Research Commission, 2016-01) Grover, B.P.C.; Johnson, R.H.; Tutu, H.Mine leachates from gold tailings impoundments usually contain elevated concentrations of metals and sulphates that impact negatively on water quality. This study was aimed at assessing the leachability of such metals from tailings by rainwater. Oxidised and unoxidised tailings were leached experimentally and through simulations using the PHREEQC geochemical modelling code. The results revealed that the majority of readily leachable metals were held in secondary mineral phases, mainly sulphates. A good agreement between experimental and modelling techniques was obtained, indicating the potential use of geochemical modelling in future metal release studies for the site. A list of reactive minerals for the tailings material was compiled. These minerals may or may not be present in the tailings; however, the list provides a means of estimating future reactivity or bulk metal release from the tailings.Item Column adsorption studies for the removal of U by phosphonated cross-linked polyethylenimine: modelling and optimization.(Springer, 2015-03) Saad, D.M.; Cukrowska, E.; Tutu, H.A continuous fixed-bed adsorption study was carried out by using phosphonated cross-linked polyethylenimine as an adsorbent for the removal of uranium (U) from aqueous solutions. The effect of inlet metal ion concentration (40, 70, and 100 mg L-1), feed flow rate (1, 2, and 3 mL min(-1)), and polymer bed height (2.5, 3.2 and 4.5 cm) on the breakthrough characteristics of the fixed-bed adsorption system at pH 2 were studied. The results showed that the breakthrough time appeared to increase with increase of bed height but decreased with increase of both influent U concentration and flow rate. Modelling of the dynamics of the fixed-bed adsorption process was studied and the application of different models to describe the breakthrough curves showed that the Thomas and Yoon-Nelson model gave better results for the operating conditions.Item Aberrant apoptotic response of colorectal cancer cells to novel nucleoside analogues.(Public Library of Science., 2015-09-21) Harmse, L.; Dahan-Farkas, N.; Panayides, J.L.; Van Otterlo, W.; Penny, C.Despite the increased understanding of colorectal cancer and the introduction of targeted drug therapy, the metastatic phase of the disease remains refractory to treatment. Since the deregulation of normal apoptosis contributes to the pathogenesis of colorectal cancer, novel nucleoside analogues were synthesized here and evaluated for their ability to induce apoptosis and cause cell death in two colorectal adeno-carcinoma cell lines, Caco-2 and HT-29. Three novel nucleoside analogues assessed here showed cytotoxic activity, as measured by the MTT assay against both cell lines: the IC50 values ranged between 3 and 37 μM, with Caco-2 cells being more sensitive than HT-29 cells. Compared to camptothecin, the positive control, the nucleoside analogues were significantly less toxic to normal unstimulated leukocytes (p>0.05). Moreover, the nucleosides were able to induce apoptosis as measured by an increase in caspase 8 and caspase 3 activity above that of the control. This was additionally supported by data derived from Annexin V-FITC assays. Despite marginal changes to the mitochondrial membrane potential, all three nucleosides caused a significant increase in cytosolic cytochrome c (p>0.05), with a corresponding decrease in mitochondrial cytochrome c. Morphological analysis of both cell lines showed the rapid appearance of vacuoles following exposure to two of the nucleosides, while a third caused cellular detachment, delayed cytoplasmic vacuolisation and nuclear abnormalities. Preliminary investigations, using the autophagic indicator monodansylcadaverine and chloroquine as positive control, showed that two of the nucleosides induced the formation of autophagic vacuoles. In summary, the novel nucleoside analogues showed selective cytotoxicity towards both cancer cell lines and are effective initiators of an unusual apoptotic response, demonstrating their potential to serve as structural scaffolds for more potent analogues.