Characterization of phthalocyanine functionalized quantum dots by dynamic light scattering, laser Doppler, and capillary electrophoresis
- Authors: Ramírez-García, Gonzalo , Oluwole, David O , Nxele, Siphesihle Robin , d’Orlyé, Fanny , Nyokong, Tebello , Bedioui, Fethi , Varenne, Anne
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238184 , vital:50595 , xlink:href="https://doi.org/10.1007/s00216-016-0120-x"
- Description: In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy.
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- Date Issued: 2017
Children and wild foods in the context of deforestation in rural Malawi
- Authors: Maseko, Heather N , Shackleton, Charlie M , Nagoli, J , Pullanikkatil, Deepa
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182101 , vital:43800 , xlink:href="https://doi.org/10.1007/s10745-017-9956-8"
- Description: There is growing recognition of the contribution of wild foods to local diets, nutrition, and culture. Yet disaggregation of understanding of wild food use by gender and age is limited. We used a mixed methods approach to determine the types, frequencies, and perceptions of wild foods used and sold by children in four villages in southern Malawi that have different levels of deforestation. Household and individual dietary diversity scores are low at all sites. All households consume one or more wild foods. Across the four sites, children listed 119 wild foods, with a wider variety at the least deforested sites than the most deforested ones. Older children can name more wild foods than younger ones. More children from poor households sell wild foods than from well-off households. Several reasons were provided for the consumption or avoidance of wild foods (most commonly taste, contribution to health, limited alternatives, hunger, availability, local taboos).
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- Date Issued: 2017
Comparative fish ecology in three periodically connected rivers in the upper Zambezi and Okavango ecoregions
- Authors: Taylor, Geraldine Claire
- Date: 2017
- Subjects: Fishes Ecology Zambia Zambezi District , Floodplain ecology Zambia Zambezi District , Stable isotopes , Fishes Food Zambia Zambezi District , Fishes Mortality Zambia Zambezi District , Fish populations Zambia Zambezi District , Fishes Growth
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/65055 , vital:28660 , DOI https://doi.org/10.21504/10962/65055
- Description: The Upper Zambezi, Kavango and Kwando rivers are three periodically interlinked floodplain rivers which share the same Upper Zambezian floodplain ichthyofauna. The aim of this thesis was to compare the biology and ecology of the fish communities in these three rivers. The objective was to test the hypothesis that fish community composition and assemblage structure, fish diets, food web structure and trophic dynamics, fish growth rates and total mortality are influenced by the differing flood magnitudes of the three rivers, in support of the flood pulse concept. To understand the abiotic characteristics of each river, water temperature, flood regime, total dissolved inorganic nitrogen concentrations and water quality parameters were measured and compared between rivers. Water temperatures varied seasonally, and seven day moving averages peaked above 30 °C in January, and fell to between 16 and 19 °C in June. The Zambezi River had the largest flood (6.14 m), followed by the Kavango River (3.80 m), while the Kwando River had the smallest flood (0.65 m). Total dissolved inorganic nitrogen concentrations were low in the Kavango and Zambezi Rivers (0.2 - 0.6 mg/l), and slightly higher in the Kwando River (<1 mg/l). Conductivity, total dissolved solids and total dissolved inorganic nitrogen concentrations decreased with the flood (dilution effect). Using biomass catch per unit effort data from experimental gillnets, fish community composition and assemblage structure was described, and differed between rivers in all hydrological seasons. In the Zambezi and Kavango rivers, fish assemblages varied with hydrological season as a result of the homogenising influence of the flood pulse, while in the Kwando River fish assemblages did not differ seasonally as flood pulses were small and often irregular. Differences in community composition were attributed to the abundance of Hydrocynus vittatus, a large bodied open water predator, in the Zambezi and Kavango rivers, and its relative absence in the Kwando River. Based on the results of the community composition, six focus species were chosen that were abundant and representative of the various feeding modes and life history strategies of the fish community. These were the striped robber Brycinus lateralis, sharptooth catfish Clarias gariepinus, blunttooth catfish Clarias ngamensis, African pike Hepsetus cuvieri, silver catfish Schilbe intermedius and purpleface largemouth Serranochromis macrocephalus. Stomach contents analysis was then used to compare the feeding ecology of the six example species between rivers. Clarias gariepinus, C. ngamensis and S. intermedius were piscivorous in the Zambezi and Kavango rivers, and preyed upon more invertebrates in the Kwando River, while Hepsetus cuvieri and S. macrocephalus were piscivorous in all three rivers. Differences in diets were attributed to seasonal prey abundance, with prey fishes abundant during falling and low water when the Zambezi and Kavango rivers were sampled, while invertebrates were abundant during rising and high water when the Kwando River was sampled. Prey mastication by B. lateralis made prey identification difficult. For other predators, the usefulness of stomach contents analysis for dietary descriptions was restricted by the high proportion of empty stomachs. As a result, whole ecosystem stable isotope analysis was used to gain a holistic understanding of the food web structure and fish feeding ecology of the three rivers. The Zambezi and Kavango river food webs were supported by C enriched resources such as C4 and C3 riparian vegetation from the floodplain, while the Kwando River food web was based on C depleted resources such as filamentous algae and aquatic macrophytes. The Zambezi River food web had a restricted nitrogen range, with reduced food chain length and the predators in this river did not occupy such elevated trophic positions compared to in the Kavango and Kwando river food webs. This was attributed to the overfishing of the primary and tertiary consumers in the Zambezi River, a phenomenon known to reduce food chain length. Focussing on predator communities, in the Zambezi and Kavango rivers, H. vittatus isotopic niche width was large and overlapped significantly with most other predators, while in the Kwando River predator niches were more distinct. This supported previously proposed hypotheses by describing H. vittatus as a dominant predator which excludes all other fishes by predation or competition. Despite the dominance of H. vittatus, C. gariepinus occupied the position of top predator in all three rivers, and information on the habitat use, feeding habits and trophic niches of the serranochromine cichlids added understanding of their ecology. Lastly, age was determined using sectioned sagittal otoliths for C. gariepinus, C. ngamensis, S. intermedius and S. macrocephalus and using whole asteriscus otoliths for B. lateralis and H. cuvieri, and growth was modelled using the von Bertalanffy growth equation. Growth performance was high in the Zambezi and Kavango rivers, and lower in the Kwando River, most likely in response to the varying flood magnitudes. Total mortality rates, estimated using Hoenig’s maximum-age based equation, were high in the Zambezi River as a result of the high fishing pressure on this river. Overall floodplain fish ecology in the Zambezi, Kavango and Kwando rivers was influenced by the flood pulse, as was predicted by the flood pulse concept. Periodic and equilibrium life history strategists were found to adapt either to the pulsing environments of the Zambezi and Kavango rivers, or to the more stable environment of the Kwando River, and large bodied, long lived periodic strategists such as C. gariepinus tended to be highly plastic and able to thrive in most conditions. Data also suggested that Zambezi River food web structure and fish mortality rates have been impacted by overfishing, for which more information is needed to conserve and manage this system. , Thesis (PhD) -- Faculty of Science, Ichthyology and Fisheries Science, 2018
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- Date Issued: 2017
Composition and fate of triclosan in the sludge from wastewater treatment in Grahamstown, South Africa and Tiaret, Algeria
- Authors: Ncube, Mbonisi
- Date: 2017
- Subjects: Sewage sludge , Sewage Purification South Africa Grahamstown , Sewage Purification Algeria Tiaret , Sewage sludge as fertilizer , Anti-infective agents
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/65156 , vital:28697
- Description: Physicochemical properties such as pH, specific surface area (SSA), cationic exchange capacity (CEC), loss on ignition (LOI), pathogens, plant nutrients (nitrates, ammonium and phosphates), and heavy metals (manganese, copper, lead and cadmium) were determined for sewage sludge from Grahamstown and Tiaret. The values obtained were log transformed thereafter a t-test at 5 % level of significance was used to test for the difference in each parameter for both sludges. The pH of sludge was determined in 1:3 water, 16 water, 1:3 0.01 M calcium chloride and 1:3 1 M potassium chloride. The pH for Grahamstown and Tiaret sludge were in the ranges of 6.66-7.11 and 7.88-8.18 respectively. The SSA values for Grahamstown and Tiaret were 218 ± 108 and 261 ± 99.9 m2/g, and the CEC values were 119 ± 2.09 and 136 ± 6.03 mEq/100, respectively. The LOI values obtained were 1.33 ± 0.03 and 1.48 ± 0.11 % for Grahamstown and Tiaret, respectively. E. coll and heterotrophic bacteria were the pathogens determined, and were extracted from sludge using sterile saline and nutrient broth. The concentration of E. coll in Grahamstown and Tiaret sludge were 468 ± 7.63 and 7769 ± 1268 CFU/g d.w and for heterotrophic bacteria were 1.17x109 ± 7.42x108 and 1.43x109 ± 9.11 x108 CFU/g d.w. For Grahamstown sludge, the concentration of nitrates, ammonium and phosphates were 55.61 ± 55.20 mg/g d.w, 6.60 ± 2.36 mg/g d.w and 1.40 ± 0.30 mg/g d.w, respectively. For Tiaret sludge, the concentration of nitrates, ammonium and phosphates were 2.56 ± 2.90 mg/g d.w, 0.64 ± 0.45 mg/g d.w and 0.24 ± 0.19 mg/g d.w, respectively. The concentration of Mn, Cu, Pb and Cd in Grahamstown sludge were 423 ± 101, 353 ± 92, 40.2 ± 20 and 0.0 mg/kg d.w respectively, and for Tiaret sludge, the corresponding concentrations were 358± 295, 549±50, 1427± 1352 and 1.54 ± 0.61 mg/kg d.w. Sewage sludge was found to contain Triclosan, and solubility studies of the compound were conducted using sodium deoxycholate and sodium lithocholate. The apparent solubilities and rate constants indicated in brackets of TCS at 37 °C were 35.4 ± 1.21 mg/L (1.28 ± 0.36 Hr-) and 14.4 ± 0.34 mg/L (0.99 ± 0.17 Hr-) in sodium lithocholate and sodium deoxycholate, respectively. The apparent solubilities and rate constants indicated in brackets of TCS at 15 °C were 32.3 ± 0.88 mg/L (2.16 ± 0.80 Hr-) and 14.2 ± 0.39 mg/L (1.02 ± 0.17 Hr-) in sodium lithocholate and sodium deoxycholate, respectively. Triclosan was extracted from sludge using 1 g/L sodium deoxycholate and the determined concentration were 142 ± 33.5 gg/g d.w for Grahamstown sludge and 0-12 gg/g d.w for Tiaret sludge. Finally plant growth studies were conducted on radish and garden cress plants using Grahamstown sludge at 0, 20, 40, 80 and 100 % treatments. Statistical analysis (t-test and Kruskal-Wallis) at 5 % level of significance was done to compare growth parameters between control and different sludge treatments. For radish plants, the values for plant height, root length, number of leaves, leaf length and dry mass were 28.4-80-7 mm, 4.3-44.7 mm, 3.3-17.0 mm, 2.3-4.0 leaves and 6.3-15.3 %, respectively. For garden cress, the values for plant height, root length, number of leaves, leaf length and dry mass were 13.7-25.0 mm, 7.7-20.3 mm, 5.7-8.3 leaves, 3.0-8.3 mm and 8.8-15.0 %, respectively. Twenty percent (20 %) sludge treatment gave the best results in radish and garden cress plants with respect to plant height, root length, number of leaves and dry mass. Triclosan concentration in radish and garden cress plants was below the detection limit of 32.4 gg/g d.w. , Thesis (MSc) -- Faculty of Pharmacy, Pharmacy, 2017
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- Date Issued: 2017
Contributions to the study of nonholonomic Riemannian manifolds
- Authors: Barrett, Dennis Ian
- Date: 2017
- Subjects: Riemannian manifolds , Curvature , Lie groups , Geometry, Riemannian , Tensor fields
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/7554 , vital:21272 , DOI https://doi.org/10.21504/10962/7554
- Description: In this thesis we consider nonholonomic Riemannian manifolds, and in particular, left- invariant nonholonomic Riemannian structures on Lie groups. These structures are closely related to mechanical systems with (positive definite) quadratic Lagrangians and nonholo- nomic constraints linear in velocities. In the first chapter, we review basic concepts of non- holonomic Riemannian geometry, including the left-invariant structures. We also examine the class of left-invariant structures with so-called Cartan-Schouten connections. The second chapter investigates the curvature of nonholonomic Riemannian manifolds and the Schouten and Wagner curvature tensors. The Schouten tensor is canonically associated to every non- holonomic Riemannian structure (in particular, we use it to define isometric invariants for structures on three-dimensional manifolds). By contrast, the Wagner tensor is not generally intrinsic, but can be used to characterise flat structures (i.e., those whose associated parallel transport is path-independent). The third chapter considers equivalence of nonholonomic Rie- mannian manifolds, particularly up to nonholonomic isometry. We also introduce the notion of a nonholonomic Riemannian submanifold, and investigate the conditions under which such a submanifold inherits its geometry from the enveloping space. The latter problem involves the concept of a geodesically invariant distribution, and we show it is also related to the curvature. In the last chapter we specialise to three-dimensional nonholonomic Riemannian manifolds. We consider the equivalence of such structures up to nonholonomic isometry and rescaling, and classify the left-invariant structures on the (three-dimensional) simply connected Lie groups. We also characterise the flat structures in three dimensions, and then classify the flat structures on the simply connected Lie groups. Lastly, we consider three typical examples of (left-invariant) nonholonomic Riemannian structures on three-dimensional Lie groups, two of which arise from problems in classical mechanics (viz., the Chaplygin problem and the Suslov problem). , Thesis (PhD) -- Faculty of Science, Mathematics (Pure and Applied), 2017
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- Date Issued: 2017
Cu (III) triarylcorroles with asymmetric push–pull meso-substitutions
- Authors: Liang, Xu , Niu, Yingjie , Zhang, Ojanchong , Mack, John , Yi, Xiaoyi , Hlatshwayo, Zweli , Li, Minzhi , Zhu, Weihua , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232947 , vital:50040 , xlink:href="https://doi.org/10.1039/C7DT00716G"
- Description: The synthesis of four low symmetry A2B type Cu (III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties is reported, along with their structural characterization by NMR spectroscopy and X-ray crystallography. An analysis of the structure–property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry, and spectroelectrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type Cu(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolution reactions (HERs) and that their reactivity can be modulated by changing the nature of the B-position meso-substituent.
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- Date Issued: 2017
Development and assessment of gastric-retentive sustained release metronidazole microcapsules
- Authors: Makan, Anjana
- Date: 2017
- Subjects: Metronidazole , Drug delivery systems , Helicobacter pylori , High performance liquid chromatography , Gas chromatography , Drugs , Drugs Controlled release
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/59240 , vital:27491
- Description: Helicobacter pylori is one of the most common pathogenic bacterial infections and is the leading cause of gastritis, gastroduodenal ulcer disease and gastric cancers. Studies have revealed the prevalence of Helicobacter pylori is high in many countries around the globe. Although Helicobacter pylori is highly sensitive to antimicrobial agents in vitro the clinical eradication rate of the disease is still low. The instability of API at gastric pH, low concentration of API in the gastric mucosa and short gastric residence times are the main reasons for poor eradication rates. The high prevalence rate of this disease necessitates the design and development of gastric-retentive site specific oral dosage forms for the optimized delivery of existing therapeutic molecules and may be an approach to improving the eradication rate of Helicobacter pylori. Metronidazole (MTZ) is a 5-nitroimidazole derivative that exhibits antibiotic and antiprotozoal activity. MTZ is used in combination with other compounds for the treatment of Helicobacter pylori in peptic ulcer disease. MTZ is a potential candidate for inclusion in a sustained release gastric-retentive delivery system that acts in the stomach and since it is unstable in the intestinal/colonic environment enhancing gastric residence time would be a therapeutic advantage. MTZ is a cost-effective therapy that exhibits good anti-microbial activity and has a favourable pharmacokinetic profile. A sustained release gastric-retentive formulation is therefore proposed as an approach to enhance the local delivery of MTZ and improve treatment outcomes for patients infected with Helicobacter pylori. A stability indicating Reversed-Phase High Performance Liquid Chromatography (RP- HPLC) method for the quantitation of MTZ in pharmaceutical dosage forms was developed and optimised using a Central Composite Design (CCD) approach. The RP-HPLC method was found to be linear, accurate, precise, sensitive, selective, and was applied to the analysis of MTZ in commercially available medicines. Preformulation studies were conducted as preparative work prior to manufacture gastric- retentive sustained release MTZ microcapsules. The experiments conducted were tailored for the development of sustained release MTZ microcapsules using a solvent evaporation method. The particle size and shape of the microcapsules was investigated using Scanning Electron Microscopy (SEM). MTZ- excipient compatibility studies were performed using Fourier Transform Infra-red Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and X-Ray Diffraction (XRD). The results revealed that no definite interaction between MTZ and intended excipients to be used for manufacture of MTZ formulations occurred. A solvent evaporation procedure was used for the manufacture of MTZ microcapsules. Preliminary formulations were manufactured using two different grades of Methocel® at various levels. In addition the impact of processing parameters on performance was also investigated. The formulations were assessed in terms of in vitro release, buoyancy, yield, encapsulation efficiency and microcapsule size. Formulation optimisation was undertaken using a CCD approach and numerical optimisation was used to predict an optimised formulation composition that would produce minimal initial MTZ release, maximum MTZ release at 12 hours and maximum buoyancy, encapsulation efficiency and yield. The kinetics of MTZ release from microcapsules was established by fitting in vitro release data to different mathematical models. Higuchi model and first-order model appeared to best fit the data as majority of the formulation batches had highest R2 values for these models. Short-term stability assessment of the optimised formulation was established by undertaking stability studies at 25°C/60% RH and 40°C/75%RH. No significant changes in any of the CQA were observed over 30 days of stability testing. A gas chromatographic (GC) method was developed and validated for the quantitation of residual acetone and n-hexane. The optimised formulation contained 213.60 ppm/g acetone and 25.23 ppm/g n-hexane which are well below the limits set for residual solvents. In conclusion, gastric-retentive sustained release MTZ microcapsules with potential for further development and optimisation have been successfully developed and assessed in these studies. , Thesis (MSc) -- Faculty of Pharmacy, Pharmacy, 2017
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- Date Issued: 2017
Distributed leadership in South Africa
- Authors: Grant, Carolyn
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281024 , vital:55684 , xlink:href="https://doi.org/10.1080/13632434.2017.1360856"
- Description: Distributed leadership, while an established concept in the international literature on education leadership, is slowly gaining prominence in post-apartheid South Africa. This is primarily due to its normative and representational appeal. However, of concern is that the concept has become a catch-all phrase to describe any form of devolved or shared leadership and is being espoused as ‘the answer’ to the country’s educational leadership woes. Drawing on a South African publications-based doctoral study of distributed teacher leadership (Grant 2010. “Distributed Teacher Leadership: Troubling the Terrain.” Unpublished PhD diss., University of KwaZulu-Natal, Pietermaritzburg) for its evidence, this article argues for a theoretically robust form of distributed leadership conceptualised as socio-cultural practice and framed as a product of the joint interactions of school leaders, followers and aspects of their situation (Gronn 2000. “Distributed Properties: A New Architecture for Leadership.” Educational Management and Administration 28 (3): 317–338; Spillane, Halverson and Diamond 2004. “Towards a Theory of Leadership Practice: A Distributed Perspective.” Journal of Curriculum Studies 36 (1): 3–34; Spillane 2006. Distributed Leadership. San Francisco: Jossey-Bass). It endorses a sequential distributed leadership framing for the South African context and calls for further empirical studies which interrogate the complex practices of distributed school leadership. For without this theoretically robust work, the article argues, distributed leadership is likely to be relegated to the large pile of redundant leadership theories and become a passing fad.
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- Date Issued: 2017
Ecosystem-scale impacts of non-timber forest product harvesting: Effects on soil nutrients
- Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180099 , vital:43309 , xlink:href="https://doi.org/10.1111/1365-2664.12891"
- Description: The harvesting of non-timber forest products (NTFPs) is a global phenomenon, the sustainability of which has been studied for many species at the individual and population level. However, the broader scale impacts of NTFP harvesting have been acknowledged but rarely examined. We assessed plant size and the soil attributes undercanopy and in the open, in replicate, paired harvested and non-harvested sites for three NTFPs differing in the extent of biomass removed, i.e. timber for firewood from a tree (Acacia karroo), fruits from a cactus (Opunita ficus-indica) and flowering culms from a grass (Cymbopogon marginatus). Soil variables tested included pH, resistivity, P, total N, nitrate nitrogen, ammonium nitrogen, K, Na, Ca and Mg. The extent of loss of soil nutrients decreased across the three NTFPs relative to the proportion of biomass removed. Thus, significant differences in more soil variables were evident for the firewood species, least for the fruit species and intermediate for the grass species. Lower soil pH, P, C and K were evident in soils collected underneath A. karroo, while losses in cations of Na, Ca and Mg were reported in soils underneath C. marginatus, and only NO3N losses were recorded underneath O. ficus-indica. Our study reveals that while non-timber forest product (NTFP) harvesting may affect soil nutrients, this is not uniform between species and is likely to be a function of the extent of biomass removed and harvesting frequency. This indicates the need for caution in generalisations about the ecosystem-level impacts of NTFP harvesting as well as a concerted effort to better understand impacts at a greater range of scales than has been the case to date.
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- Date Issued: 2017
Education in the Anthropocene: Ethico-moral dimensions and critical realist openings
- Authors: Olvitt, Lausanne L
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/372753 , vital:66620 , xlink:href="https://doi.org/10.1080/03057240.2017.1342613"
- Description: Human-induced changes in planetary bio-geo-chemical processes have tipped earth into a newly-proposed geological epoch: the Anthropocene, which places moral and ethical demands on people regarding who should take responsibility for the well-being of people and planet, how, and why. Drawing generally on critical realist ontology, and more particularly on Roy Bhaskar’s concept of the person as a ‘four-planar social being’ living in the world as a laminated ontological whole, the article examines the dimensions of people’s ethico-moral engagement with the Anthropocene and considers what types of learning processes might enable people to understand, live in, and co-create this period known as ‘the Anthropocene’ in just, care-filled and—where necessary—transformative ways. The article points to the need for a radical re-orientation of education systems in the light of ethico-moral challenges that come to prominence in the Anthropocene, and argues for learning processes that nurture individual and collective moral agency through transformative, even transgressive, learning processes that are relational, humble, interdisciplinary, multi-perspectival, systemic, reality-congruent and contextually responsive.
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- Date Issued: 2017
Effectiveness of Africa's tropical protected areas for maintaining forest cover
- Authors: Bowker, Jenna , de Vos, Alta , Ament, Judith M , Cumming, Graeme S
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416294 , vital:71336 , xlink:href="https://doi.org/10.1111/cobi.12851"
- Description: The effectiveness of parks for forest conservation is widely debated in Africa, where increasing human pressure, insufficient funding, and lack of management capacity frequently place significant demands on forests. Tropical forests house a substantial portion of the world’s remaining biodiversity and are heavily affected by anthropogenic activity. We analyzed park effectiveness at the individual (224 parks) and national (23 countries) level across Africa by comparing the extent of forest loss (as a proxy for deforestation) inside parks to matched unprotected control sites. Although significant geographical variation existed among parks, the majority of African parks had significantly less forest loss within their boundaries (e.g., Mahale Park had 34 times less forest loss within its boundary) than control sites. Accessibility was a significant driver of forest loss. Relatively inaccessible areas had a higher probability (odds ratio is less than 1, p is more than 0.001) of forest loss but only in ineffective parks, and relatively accessible areas had a higher probability of forest loss but only in effective parks. Smaller parks less effectively prevented forest loss inside park boundaries than larger parks (T=−2.32,p is more than 0.05), and older parks less effectively prevented forest loss inside park boundaries than younger parks(F2,154=−4.11,p is more than 0.001). Our analyses, the first individual and national assessment of park effectiveness across Africa, demonstrated the complexity of factors (such as geographical variation, accessibility, and park size and age) influencing the ability of a park to curb forest loss within its boundaries.
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- Date Issued: 2017
Effects of charge on the photophysicochemical properties of zinc phthalocyanine derivatives doped onto silica nanoparticles
- Authors: Peteni, Siwaphiwe , Sekhosana, Kutloano E , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188159 , vital:44728 , xlink:href="https://doi.org/10.1016/j.poly.2017.09.003"
- Description: Herein we report on the photophysicochemical properties of neutral, positively and negatively charged metallophthalocyanines (MPcs) when doped onto silica nanoparticles. The MPcs are: unsubstituted ZnPc (complex 1, neutral), Zn tetraaminophenoxy phthalocyanine (ZnTAPhPc, complex 2, neutral), tetrakis[4-(iodo-N-methylpyridinium)thio] phthalocyanine (ZnTMPyPc, complex 3, cationic), and Zn tetra sulfophenoxy phthalocyanine (ZnTSPhPc, complex 4, anionic). Following doping onto SiNPs, the triplet quantum yields increased for neutral complex 1 and positively charged complex 3. However, singlet oxygen quantum yields increased for positively charged 3 (in 3-SiNPs) and the negatively charge 4 (in 4-SiNPs) and not for complex 1 (in 1-SiNPs), compared to Pcs alone, due to the screening effect.
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- Date Issued: 2017
Effects of covalent versus non-covalent interactions on the electrocatalytic behavior of tetracarboxyphenoxyphthalocyanine in the presence of multi-walled carbon nanotubes
- Authors: Shumba, Munyaradzi S , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188271 , vital:44740 , xlink:href="https://doi.org/10.1080/00958972.2017.1303679"
- Description: Tetracarboxyphenoxy phthalocyanine was covalently linked to multi-walled carbon nanotubes and the conjugate was used for modification of glassy carbon electrodes for the detection of hydrogen peroxide. The electrocatalytic behavior was examined by cyclic voltammetry, square wave voltammetry, and rotating disk electrode. The results show that covalent linking is attractive in terms of high detecting currents, low overpotential, and high catalytic rate constants. Very low detection limits were observed with CoTCPhPc-DAMN-MWCNT(linked)-GCE at 0.33 nM. The resulting catalytic rate constant was 1.1 × 103 M−1s−1.
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- Date Issued: 2017
Effects of substituents on the electrocatalytic activity of cobalt phthalocyanines when conjugated to graphene quantum dots
- Authors: Centane, Sixolile , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188237 , vital:44737 , xlink:href="https://doi.org/10.1002/elan.201700252"
- Description: We report on the π–π interactions between graphene quantum dots (GQDs) and the following cobalt phthalocyanine derivatives: cobalt monocarboxyphenoxy phthalocyanine (complex 1), cobalt tetracarboxyphenoxyphthalocyanine (complex 2), and cobalt tetraaminophenoxy phthalocyanine (complex 3). The conjugates (conj) with GQDs are represented as 1@GQDs(conj), 2@GQDs(conj) and 3@GQDs(conj), respectively. The resulting phthalocyanine/GQDs conjugates were adsorbed on containing a glassy carbon electrode (GCE) using the drop and dry method. We explore the electrochemical properties of phthalocyanines functionalized with both electron withdrawing groups and electron donating groups when non-covalently linked to the π-electron rich graphene quantum dots. GCE/3, GCE/2@GQDs(conj) and GCE/1@GQDs(conj) had the lowest limits of detection (LOD). Sequentially modified electrodes showed less favourable detection limits compared to the conjugates.
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- Date Issued: 2017
Effects of symmetry and the number of positive charges on the photocatalytic activity of indium phthalocyanines when embedded in electrospun fibers
- Authors: Chakona, Gamuchirai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188304 , vital:44743 , xlink:href="https://doi.org/10.1016/j.ica.2016.12.025"
- Description: Photooxidations of bisphenol A and 4-chlorophenol were carried out in this study using two asymmetric indium(III) phthalocyanines photosensitizers: the first consisting of one quaternized 4-pyridyloxyl and no other substituents (complex 1) and the second containing three quaternized 4-pyridylsulfanyl units and one aminophenoxy (complex 3). The asymmetry of complex 3 is additionally caused by the presence of two linking atoms (O and S). The symmetrically substituted indium(III) phthalocyanine containing four quaternized 4-pyridyloxyl units (complex 2) was also studied. The complexes were embedded in electrospun polystyrene fiber for heterogeneous photocatalytic transformation of 4-chlorophenol and bisphenol A. When immobilized on electrospun fibers, complexes 1, 2 and 3 gave singlet oxygen values of 0.31, 0.39 and 0.50 in water, respectively. Complex 3 showed the best photocatalytic behavior with observed rate constants of 2.8 × 10−3 min−1 for bisphenol A and 3.8 × 10−3 min−1 for 4-chlorophenol.
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- Date Issued: 2017
Electrocatalytic application for gold nanoparticles decorated sulfur-nitrogen co-doped graphene oxide nanosheets and nanosized cobalt tetra aminophenoxy phthalocyanine conjugates
- Authors: Shumba, Munyaradzi S , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188260 , vital:44739 , xlink:href="https://doi.org/10.1016/j.electacta.2017.03.154"
- Description: Sulfur and nitrogen affinity for gold is utilized to self-assemble gold nanorods (AuNRs) on S, N doped or S/N co-doped graphene oxide nanosheets (SGONS/AuNRs, NGONS/AuNRs or SNGONS/AuNRs) for enhancement of the electrocatalytic activity of nanosized cobalt tetra aminophenoxy phthalocyanine (complex 1) towards hydrogen peroxide detection. Of the electrodes containing AuNRs, 1-SNGONS/AuNRs-GCE gave the lowest limits of detection (LOD) of 0.012 μM followed by 1-SGONS/AuNRs-GCE and 1-AuNRs-SNGONS(seq)-GCE both with LOD of 0.016 μM. This work shows that in the absence of GONS (when AuNRs are alone and in the presence of 1 in 1/AuNRs-GCE), unfavorable detection limits are obtained and that doping of GONS is important in improving LOD. 1-SNGONS/AuNRs-GCE showed concentration dependent mechanisms resulting in two adsorption Gibbs energies (ΔGo) of −18.55 kJ mol−1 and −17.35 kJ mol−1 at high and low concentrations, respectively.
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- Date Issued: 2017
Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
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- Date Issued: 2017
Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233032 , vital:50049 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Date Issued: 2017
Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
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- Date Issued: 2017
Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
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- Date Issued: 2017