Successes and challenges of women's income generating projects in Zimbabwe
- Authors: Hamunakwadi, Purity
- Date: 2016
- Subjects: Women in development -- Zimbabwe , Women -- Employment -- Zimbabwe , Economic development projects -- Zimbabwe , Women in rural development -- Zimbabwe
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10948/6810 , vital:21145
- Description: Women’s income-generating projects are regarded as a critical area in promoting sustainable livelihoods in the lives of the poor. This study centres on a cattle project in Sadomba village in Nyanga District, Zimbabwe. The purpose of this study is to investigate the role and contributions of income-generating projects with regard to women; the necessary conditions for a successful cattle production project; the major challenges in women’s income-generating projects, and how income-generating projects can be strengthened, all in relation to this cattle project.The study is underpinned by the sustainable livelihood approach and literature on micro-financing of women’s projects in various countries. The study is based on qualitative methodology using a case study design and methods of data collection included semi-structured interviews, focus group discussions and participant observation. The data was analysed using thematic analysis and sub-themes that arose in the study and thereafter all the data was grouped by a process of coding. The results indicated that the Sadomba cattle project has benefited the project members in terms of income generation by the selling of cattle and milk, for agricultural purposes (draught power) and also income they obtained from hiring their cattle to other community members in rainy seasons. The income generated has assisted them to send their children to school and attain higher education.In addition, it promotes community engagement when they share paddocks and dip tanks. However, despite these benefits, they face a number of challenges such as long distances to the market, a lack of microcredit and the unavailability of exotic breeds. Therefore, there is need to integrate the conditions that are necessary for successful income generating projects to the Sadomba cattle project.
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- Date Issued: 2016
Supra-maximal speed interval training effect on a 40m standing start sprint and timed 3000m running performance in moderately trained female runners: Alterg anti-gravity treadmill running
- Authors: Ellerbeck, Tim
- Date: 2016
- Subjects: Interval training , Women runners , Running -- Training
- Language: English
- Type: Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10948/6772 , vital:21140
- Description: The purpose of this study was to explore what the supra-maximal speed interval training effect was on a 40m standing start sprint and timed 3000m running performance was for two separate study groups when using either the AlterG® anti-gravity treadmill, or downhill running as a training intervention, for moderately trained female runners. The level of delayed onset of muscle soreness (DOMS) after each supra-maximal speed interval session was also captured. Data from 20 women was collected during initial pre-intervention testing; involving the 40m standing start sprint and 3000m timed trial run. During a four week training intervention the level of DOMS experienced by participants at increments of 24 hours, 48 hours and 72 hours, in each respective training group was recorded. Post-intervention testing was performed to once again measure the participants 40m standing start sprint and 3000m timed trial run values, results were analysed and compared to pre-intervention data.
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- Date Issued: 2016
Surface characteristics of rock glaciers in the Jutulsessen, Dronning Maud Land, Antarctica
- Authors: Rudolph, Elizabeth Magdalena
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/2667 , vital:20314
- Description: Rock glaciers are landforms that present downslope movement of debris under the influence of ice and gravity. These landforms can be used as paleo-climate indicators as well as proxies for climate change. Rock glaciers have been investigated in a variety of climates and landscapes, however continental Antarctica, Dronning Maud Land specifically, remains understudied. This thesis aimed to investigate and classify five rock glaciers observed in the Jutulsessen, Dronning Maud Land. The surface characteristics and geomorphology were assessed and used as generic classifiers. Size, shape and landscape association was established by field surveying and GIS, whilst sediment and clast characteristics were determined from sampling. A surface temperature profile was created from short-term high frequency temperature measurements. All of the rock glaciers exhibit either undulating surfaces or patterned ground, or both, which suggests active-layer related processes. Sediment particle size analysis is inconclusive. The 137Cs-content and fabric analysis suggest movement regimes similar to other rock glaciers with higher activity at the head, and variable movement directions at the toe. Relative “activeness” is inferred from morphology: Grjotlia, Grjotøyra and Vassdalen were classified as lobate, spatulate and tongue-shaped respectively with Grjotlia the most stable. A new morphological classification of ‘crown-shaped’ is suggested for Brugdedalen and Jutuldalen, and they also appear most active. The control of local climate on rock glacier mechanics is emphasised by the findings, and thus climatic interpolation from a single weather stations is not useful. Increased spatial and temporal coverage of sediment profiles, surface topography and active-layer characteristics could be used to elucidate the processes and controls of these landforms in the Antarctic.
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- Date Issued: 2016
Surfing the waves of learning: enacting a Semantics analysis of teaching in a first-year Law course
- Authors: Clarence, Sherran
- Date: 2016
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59816 , vital:27654 , https://doi.org/10.1080/07294360.2016.1263831
- Description: Students’ ability to build knowledge, and transfer it within and between contexts is crucial to cumulative learning and to academic success. This has long been a concern of higher education research and practice. A central part of this concern for educators is creating the conditions that enable their students' deep learning, as this is an area of significant struggle for many students. Legitimation Code Theory, in particular the dimension of Semantics, is proving useful in examining the kinds of conditions that may be necessary for students to build disciplinary knowledge cumulatively over time. Using illustrative data from one case study, this paper suggests that the conceptual tools offered by Semantics can provide academic lecturers and academic development staff with a set of conceptual and analytical tools which can enable them to ‘see’ and understand the ways in which knowledge can be cumulatively acquired and used, as well as the possible gaps between what they are teaching and what their students may be learning. The hope is that these new insights will provide new directions for change in teaching and learning where these may be needed.
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- Date Issued: 2016
Sustainble public bus transport services in the Nelson Mandela Bay
- Authors: Mntwini, Mkhonto
- Date: 2016
- Subjects: Urban transportation -- Economic aspects Urban transportation -- Research Transportation -- Customer services
- Language: English
- Type: Thesis , Masters , MBA
- Identifier: http://hdl.handle.net/10948/11875 , vital:27000
- Description: Purpose - Transport is a common constant variable found in just about every aspect of our lives as well as commercial activities; this is so because transport enables accessibility to people, places and goods. The effective management of public passenger transport operations is a more complex and all-embracing concept than what it may appear at first glance. Wider dispersed work place locations and urban sprawl is on the rise driven by among other factors the increased rate of globalisation. A unique opportunity is then presented in a developing country like South Africa for effective planning and management of public passenger bus operations. In the main, the purpose of this case study research was to develop a more sustainable public passenger transport bus operation to better connect people, places and goods. The organisation that will be studied is Blunden Coach Tours a luxury and semi-lux coach Tour operator, operating from the Nelson Mandela Bay. Design / Methodology / Approach – This study employed the case study research approach which was based on the qualitative research paradigm as such allowed for in-depth description and analysis of the case as well as related phenomena in real world context. The researcher focused only on the public passenger bus transport operations in Nelson Mandela Bay thus assuming a single context focus with a single case namely the development of a more sustainable public passenger transport operations in Nelson Mandela Bay. An embedded multiple unit of analysis strategy was employed selecting a sample of key persons responsible for strategic operational areas at Blunden Coach tours, sub-contractors and suppliers. The case study employed an in-depth probing interview process in an effort to better comprehend occurrences within the actual context of the events observed. The secondary sources of information gathered were used to structure and backup the interview questions. Practical implications – The case study enabled thought provoking insight which by virtue of South Africa’s historical socio-economic landscape offered an unusual perspective of the South African bus transport scene with a particular focus on environmental, regulatory and socio-economic sustainability considerations. A limitation to the study – The lack of responses to the interview questions from some of the key role players in the bus industry who were contacted as well as some of the respondents interviewed. The lack of responses to some of the interview questions could be perceived as a limitation to validating the Summary drawn from the study.
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- Date Issued: 2016
Swazi oral literature, eco-culture and environmental apocalypse
- Authors: Enongene Mirabeau Sone
- Date: 2016
- Subjects: Swazi oral literature; eco-culture; eco-literature; eco-criticism; environmental sustainability
- Language: English
- Type: Journal Article
- Identifier: http://hdl.handle.net/11260/2632 , vital:42302
- Description: The main objective of this paper is to show how oral literature is engaged by Swazis with regards to environmental sustainability. It demonstrates the relationship between nature and culture as reflected in Swazi oral literature and how indigenous knowledge embedded in this literature can be used to expand the concepts of eco-literature and eco-criticism. The paper argues that the indigenous environmental expertise among the Swazi people, encapsulated in their oral literature, can serve as a critical resource base for the process of developing a healthy environment. Furthermore, the paper contends that eco-criticism, which is essentially a Western concept, can benefit by drawing inspiration from the indigenous knowledge contained in Swazi culture and expressed in their oral literature. The paper concludes by recommending the need to strengthen traditional and customary knowledge and practices by protecting and recognizing the values of such systems in the conservation of biodiversity for sustainable development
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Synthesis and biological evaluation of novel thiazole-based compounds
- Authors: Olawode, Emmanual Oladayo
- Date: 2016
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/62955 , vital:28325
- Description: Thesis embargoed for one-year period. Expected date of release: April 2019
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- Date Issued: 2016
Synthesis and characterisation of lanthanide complexes with nitrogen- and oxygen-donor ligands
- Authors: Madanhire, Tatenda
- Date: 2016
- Subjects: Rare earth metals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/13127 , vital:27154
- Description: The reactions of Ln(NO3)3∙6H2O (Ln = Pr, Nd or Er) with the potentially tridentate O,N,O chelating ligand 2,6-pyridinedimethanol (H2pydm) were investigated, and complexes with the formula, [Ln(H2pydm)2(NO3)2](NO3) (Ln = Pr or Nd) and [Er(H2pydm)3](NO3)3 were isolated. The ten-coordinate Pr(III) and Nd(III) compounds crystallise in the triclinic space group P-1 while the nine-coordinate Er(III) complex crystallises in the monoclinic system (P21/n). The reaction of PrCl3∙6H2O with H2pydm yielded the compound, [Pr(H2pydm)3](Cl)3, that crystallises in the monoclinic system, space group P21/c with α = 90, β = 98.680(1) and γ = 90°. The nine-coordinate Pr(III) ion is bound to three H2pydm ligands, with bond distances Pr-O 2.455(2)-2.478(2) Å and Pr-N 2.6355(19)-2.64(2) Å. X-ray crystal structures of all the H2pydm complexes reveal that the ligand coordinates tridentately, via the pyridyl nitrogen atom and the two hydroxyl oxygen atoms. The electronic absorption spectra of complexes show 4f-4f transitions. Rare-earth complexes, [Ln(H2L1)2(NO3)3] [Ln = Gd, Ho or Nd], were also prepared from a Schiff base. The X-ray single-crystal diffraction studies and SHAPE analyses of the Gd(III) and Ho(III) complexes shows that the complexes are ten-coordinate and exhibit distorted tetradecahedron geometries. With proton migration occurring from the phenol group to the imine function, complexation of the lanthanides to the ligand gives the ligand a zwitterionic phenoxo-iminium form. A phenolate oxygen-bridged dinuclear complex, [Ce2(H2L1)(ovan)3(NO3)3], has been obtained by reacting Ce(NO3)3∙6H2O with an o-vanillin derived Schiff base ligand, 2-((E)-(1-hydroxy-2-methylpropan-2-ylimino)methyl)-6-methoxyphenol (H2L1). Hydrolysis of the Schiff base occurred to yield o-vanillin, which bridged two cerium atoms with the Ce∙∙∙Ce distance equal to 3.823 Å. The Ce(III) ions are both tencoordinate, but have different coordination environments, showing tetradecahedron and staggered dodecahedron geometries, respectively. The reaction of salicylaldehyde-N(4)-diethylthiosemicarbazone (H2L2) in the presence of hydrated Ln(III) nitrates led to the isolation of two novel compounds: (E)-2[(ortho-hydroxy)benzylidene]-2-(thiomethyl)-thionohydrazide (1) and bis[2,3-diaza4-(2-hydroxyphenyl)-1-thiomethyl-buta-1,3-diene]disulfide. The latter is a dimer of the former. For this asymmetric Schiff base, 1 and the symmetric disulfide, classical hydrogen bonds of the O–H∙∙∙N as well as N–H∙∙∙S (for 1) type are apparent next to C–H∙∙∙O contacts. 4-(4-Bromophenyl)-1-(propan-2-ylidene)thiosemicarbazide was also prepared upon reacting 4-(4-bromophenyl)-3-thiosemicarbazide with acetone in the presence of ethanol and La(NO3)3∙6H2O. The C=S bond length was found to be 1.6686(16) Å which is in good agreement with other thioketones whose metrical parameters have been deposited with the Cambridge Structural Database. Classical hydrogen bonds of the N–H∙∙∙N and the N–H∙∙∙Br type are observed next to C–H∙∙∙S contacts. All synthesised compounds were characterised by microanalyses, single-crystal X-ray diffraction (except for [Nd(H2L1)2(NO3)3]), 1H NMR and IR spectroscopy.
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- Date Issued: 2016
Synthesis and characterization of group 12 dithiolate complexes as single source precursors for the preparation of hexadecylamine capped metal sulfide nanoparticles and polymer
- Authors: Osuntokun, Jejenija
- Date: 2016
- Subjects: Nanotechnology Nanoparticles Semiconductors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10353/14060 , vital:39801
- Description: A series of heteroleptic mixed ligand complexes of some alkyl substituted thiourea, tetramethyl thiuram disulfide and 1-cyano-1-carboethoxy-2,2 ditholate of Zn(II) Cd(II) and Hg(II) have been synthesized by stoichiometry reactions of the ligands with respective metal salts. They have been characterized with analytical and spectroscopic techniques. Seven out of the 19 complexes synthesized are pyridine 2, 2 bipyridine and 1, 10 phenanthroline adducts of dissopropyl parent adducts of Zn(II) and Cd(II) complexes. All the complexes are proposed as four coordinate except the pyridine adducts, 2, 2’ bipyridine and 1, 10 phenanhroline adducts that are proposed as five and six coordinate respectively. All the complexes are solid, air stable and moisture stable for a many months. They are not soluble in common organic solvents but partially soluble in coordinating solvents like DMF and DMSO and due to their insolubility problems all attempts to grow single crystal of the complexes proved abortive. The complexes gave respective metal sulfide on thermal decomposition in TGA and this makes them to be potentially useful single source precursor for the synthesis of metal sulfide. All the complexes were invariably thermolysed in HDA to synthesis a series of HDA-capped ZnS, CdS and HgS nanoparticles. The optical properties of the nanoparticles reveal that they are all blue-shifted from the absorbance edge and this confirms quantum confinement of the nanoparticles. The transmittance electron microscope showed that the nanoparticles are in nanodimension. ZnS nanoparticles from the pyridine adducts gave HDA-capped ZnS nanoparticles with a mixture of hexagonal and cubic phases while the HDA capped CdS from the 2, 2 bipyridine and 1,10 phenanthroline gave anisotropic nanoparticles. The sizes of the CdS from the 1,10 phenanthroline adducts were also found to be biggest while CdS nanoparticles from 2,2 bipyridine adduct were also revealed to be bigger than the particle sizes obtained from the parent complex, (1-cyano-1 carboethoxyethylene-2,2-dithiolato- κ,S’S)-bis(N, N’-diisopropylthiourea -κS)cadmium(II). ZnS and CdS polymer encapsulated nanocomposites were also synthesized using a solution casting method. The polymers employed were; Polymethyl metharcrylate (PMMA), Poly(vinly alcohol) (PVA), and poly vinyl pyrrolidone (PVP). The structural and thermal properties of the pure polymers and the respective nanocomposites were investigated. It was observed that the ZnS/PVA and CdS/PVA were the most thermally stable composites when the thermal stability of the pure polymers were compared relative to the nanocomposites using data obtained from thermal decomposition results of the TGA.
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- Date Issued: 2016
Synthesis and dark toxicity of 5-(4-carboxyphenyl)-10, 15, 20-tris (phenyl)-porphyrinato chlorido gallium (III) when conjugated to δ-aminolevulinic acid
- Authors: Managa, Muthumuni , Mkhize, Scebi , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240014 , vital:50789 , xlink:href="https://doi.org/10.1080/00958972.2016.1223292"
- Description: 5-(4-Carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato chlorido gallium(III) (2) was synthesized and then linked to ethyl ester δ-aminolevulinic acid to form 3. There was no shift in Soret band following conjugation. The fluorescence and singlet oxygen generating behavior of the porphyrins were also investigated. The highest singlet oxygen quantum yield (ΦΔ) obtained was that of 3. Complexes 2 and 3 as well as metal free 5-(4-carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato showed no dark toxicity on MCF-7 breast cancer cells.
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- Date Issued: 2016
Synthesis and evaluation of substituted 4-(N-benzylamino)cinnamate esters as potential anti-cancer agents and HIV-1 integrase inhibitors
- Authors: Faridoon, H , Edkins, Adrienne L , Isaacs, Michelle , Mnkandhla, Dumisani , Hoppe, Heinrich C , Kaye, Perry T
- Date: 2016
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/66289 , vital:28929 , https://doi.org/10.1016/j.bmcl.2016.05.023
- Description: publisher version , Encouraging selectivity and low micromolar activity against HeLa cervical carcinoma (IC50 ⩾ 3.0 μM) and the aggressive MDA-MB-231 triple negative breast carcinoma (IC50 ⩾ 9.6 μM) cell lines has been exhibited by a number of readily accessible 4-(N-benzylamino)cinnamate esters. The potential of the ligands as HIV-1 integrase inhibitors has also been examined.
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- Date Issued: 2016
Synthesis and exploration of resorcinol derivatives as Plasmodium falciparum Hsp90 inhibitors
- Authors: Umumararungu, Théoneste
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/717 , vital:19984
- Description: In this research project, we have synthesized a series of nine dimethyl ether resorcinol analogues of NMS-E973 (L-1) 38, a potent Hsp90 inhibitor. These analogues were chosen because they share the same pharmacophore with NMS-E973 (L-1) 38 and were thus expected to have a similar biological activity. Moreover, it is generally easier to synthesize the dimethyl ether resorcinol analogues of NMS-E973 (L-1) 38 as compared to their demethylated counterparts. Since other Hsp90 inhibitors such as geldanamycin 19 have demonstrated anti-plasmodial activity, we also expected our compounds to be Hsp90 inhibitors and to possess anti-plasmodial activity. However, our compounds were tested for growth inhibitory activity of Plasmodium falciparum and not for P. falciparum Hsp90 (PfHSP90) inhibitory activity. The synthesis involved a series of steps that led to the formation of the ester compound TU-011 (L-7) 43 that was then used as a precursor for different NMS-E973 (L-1) 38 analogues. The choice of analogues to be synthesized was dictated by binding affinity predictions obtained from molecular docking. The chosen synthetic analogues were active against chloroquine-sensitive Plasmodium falciparum (3D7 strain) in a Plasmodium lactate dehydrogenase assay and they were not generally cytotoxic to human cervical adenocarcinoma cell line HeLa. The most active of our compounds was TU-018 (L-103) 50 with an IC50 value of approximately 1.830 µM as compared to the standard, chloroquine, with an IC50 value of 0.01062 µM. Some of the compounds showed mild cytotoxicity towards HeLa cells with IC50 values higher than 25 µM as compared to the standard apoptosis inducer drug, emetine that had an IC50 value of 0.09948 µM. These results highlight the fact that the synthesized analogues are novel relatively non-toxic anti-plasmodial agents.
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- Date Issued: 2016
Synthesis and optical limiting properties of new lanthanide bis-and tris-phthalocyanines
- Authors: Sekhosana, Kutloana Edward , Manyeruke, Meloddy Hlatini , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240063 , vital:50795 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.05.068"
- Description: This manuscript reports on syntheses of new multi-decker phthalocyanines, namely: bis-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} cerium(III) (2), tris-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} dicerium(III) (4) and bis-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} gadolinium(III) (5). Complex 4 which is a tris phthalocyanine showed better nonlinear optical behavior in solution than 2 which is a bis phthalocyanine, both containing the same central metal, Ce. All the three molecules possess good optical limiting properties judged by the limiting threshold values which ranged from 0.04 to 0.09 J cm−2 with complex 5 embedded in thin films, showing the lowest value of 0.04 J cm−2. Furthermore, nonlinear optical processes responsible for reverse saturable absorption data are investigated.
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- Date Issued: 2016
Synthesis and photophysicochemical properties of BODIPY dye functionalized gold nanorods for use in antimicrobial photodynamic therapy
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
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- Date Issued: 2016
Synthesis and physicochemical properties of zinc and indium phthalocyanines conjugated to quantum dots, gold and magnetic nanoparticles
- Authors: Osifeko, Olawale , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188639 , vital:44771 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.04.015"
- Description: This work reports on the conjugation of semiconductors quantum dots (QDs), gold (AuNPs) or Fe3O4 magnetic (MNPs) nanoparticles to 4-(4,6-diaminopyrimidin-2-ylthio) substituted indium or zinc phthalocyanines (Pcs). The QDs and MNPs were linked to the Pcs via an amide bond and by chemisorption unto AuNP surface. There is a general decrease in fluorescence quantum yields of the Pcs in the presence of all the nanoparticles. There is an increase triplet quantum yields for Pcs in the presence of AuNPs and QDs, but not in the presence of MNPs. AuNPs conjugates irrespective of the central atoms have the highest singlet oxygen quantum yield and are more photo-stable than all the other conjugates. MPcs are less photostable in the presence of MNPs.
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- Date Issued: 2016
Synthesis and singlet oxygen production by a phthalocyanine when embedded in asymmetric polymer membranes
- Authors: Mafukidze, Donovan M , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188563 , vital:44765 , xlink:href="https://doi.org/10.1016/j.polymer.2016.10.032"
- Description: 2(3), 9(10), 16(17), 23(24)-Tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (ClInTAPPc, 3) was first conjugated to two different polymers: polystyrene (PS) and polyacrylonitrile (PAN) to form 3-PS and 3-PAN. The conjugates were cast into the corresponding polymers to form membranes represented as 3-PS-membrane and 3-PAN-membrane, respectively. The prepared membranes were characterized using various techniques including scanning electron microscopy and solid state UV/Vis spectroscopy. Singlet oxygen quantum yields were higher for the 3-PS-membrane at 0.51 compared to 3-PAN-membrane at 0.35. The larger singlet oxygen also applies to 3-PS (0.63) compared to 3-PAN (0.38) when in solution.
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- Date Issued: 2016
Synthesis and structural studies of NiS and PdS nanoparticles/nanocomposites from dithiocarbamates single source precursors
- Authors: Nqombolo, Azile
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11359 , http://hdl.handle.net/10353/d1021326
- Description: The main aim of this research is to synthesize Ni(II) and Pd(II) dithiocarbamate complexes and use them as single source precursors for the synthesis of NiS and PdS nanoparticles and metal sulphides potato starch nanocomposites. Four dithiocarbamate ligands were synthesized and characterized using elemental analysis and spectroscopic techniques. The ligands were used to prepared homoleptic Ni(II) and Pd(II) complexes of the dithiocarbamate ligands. The metal complexes were characterized with elemental analysis, UV-Vis, FTIR and 1H-NMR spectroscopic techniques. Conductivity measurements indicate that all the complexes are non-electrolytes in solution and results from the electronic spectra studies confirmed the proposed 4-coordinate square planar geometry around the metal ions. The nickel complexes showed d-d transitions around 477 nm while in the palladium complexes, no d-d transitions were observed but the compounds showed strong metal to ligand charge transfer transitions. From the FTIR spectra studies, it can be confirmed that the complexes were successfully synthesised because all peaks of interest were observed at expected regions from the literature. The νC-N was observed around 1469-1495 cm-1, νC=S around 1101-1188 cm-1 and νC-S around 738-1060 cm-1 for both Ni(II) and Pd(II) complexes. νNi-S was observed around 375-543 cm-1 and νPd-S around 529-545 cm-1. The FTIR also confirmed that the dithiocarbamate ligands act as bidentate chelating ligands through the sulfur atoms. The complexes were used as single source precursors and thermolysed in hexadecylamine (HDA) at 220 °C to prepare four HDA-capped nickel sulfide nanoparticles and four palladium sulfide nanoparticles. The as-prepared nanoparticles were studied with optical absorption spectra, photoluminescence, powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The optical studies results showed that NiS have large band gaps that are greater than that of the bulk, therefore they are found to be blue shifted relative to the bulk, which shows that they have small particle size and thus confirming their quantum confinement effect. PL spectra reveal that the emission peaks are red shifted compared to the absorption band edges of the nanoparticles. The XRD patterns confirmed the formation of cubic and rhombohedral phase for NiS nanoparticles and cubic phase for PdS nanoparticles. SEM images of both NiS and PdS show uniform surface morphology at low and high magnification with different shapes. EDS analyses confirmed the presence of Ni, S, and Pd in each of the spectrum indicating that the nanoparticles were successfully synthesized. TEM images showed that the synthesised nanoparticles have uniform and narrow size distribution with no agglomeration. The sizes of the NiS nanoparticles were found to be in the range of 12-38 nm for NiS1, 8-11 nm for NiS2, 9-16 nm for NiS3 and 4-9 nm for NiS4. The TEM images for the as-prepared PdS nanoparticles showed that the average crystallite sizes are 6.94-9.62 nm for PdS1, 8-11 nm for PdS2, 9-16 nm for PdS3 and 4-9 nm for PdS4 respectively. The nanoparticles were used to prepare potato starch nanocomposites and SEM images indicate that the surface morphology of starch polymer nanocomposites compose of potato starch and few particles in between the pores of the matrix, this is due to the small ratio of nanoparticles used.
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- Date Issued: 2016
Synthesis of chiral ketopinic acid-derived catalysts and their evaluation in asymmetric transformations
- Authors: Hassan, Yusuf
- Date: 2016
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/550 , vital:19969
- Description: Four new (+)-ketopinic acid-derived Mn(III) complexes, three of which possess pseudo C2- symmetry, were synthesised as chiral catalyst candidates. The ligands were prepared by refluxing (+)-ketopinic acid with ethane-1,2-diamine, the resolved (R,R)- and (S,S)-1,2-diaminocyclohexanes, and 1,2-diaminobenzene in chloroform. Treatment of the ligands with manganese(II) acetate tetrahydrate in refluxing ethanol afforded the respective complexes as brown amorphous powders. Characterisation of the ligands and the corresponding complexes was achieved using 1-D and 2-D NMR, IR spectroscopy, and elemental analysis. Various homogeneous asymmetric transformations, were investigated using these four complexes, viz., aldol, and Baylis-Hillman reactions, aza-Michael addition of piperidine to the Baylis-Hillman adducts, epoxidation, and ketone and imine reduction. Asymmetric aldol reactions of benzaldehyde with the aryl ketones, acetophenone, propiophenone, -tetralone, 4-nitroacetophenone, and 4-methoxyacetophenone, conducted in the presence of 10 mole % of the chiral catalysts, afforded enantioselectivities of up to 99% e.e. Asymmetric Baylis-Hillman reactions of methyl- and tert-butyl acrylates with pyridine-2- carbaldehyde, 6-methylpyridine-2-carbaldehyde, 5-chlorosalicylaldehyde, benzaldehyde, 4-chlorobenzaldehyde, and 2-nitrobenzaldehyde were conducted in the presence of catalyst 139 (10 mole %) to afford enantioselectivities of up to 44% e.e. Aza-Michael addition of piperidine to racemic Baylis- Hillman adducts in the presence of the catalyst 139 (10 mole %) was found to proceed with diastereoselectivities of up to 91% d.e. Asymmetric epoxidation of trans-methyl styrene, styrene, trans-stilbene, cis-stilbene, and indene, using a 5 mole % chiral catalyst loading and m-CPBA as the oxygen source, gave enantioselectivities of up to 32 % e.e. Asymmetric reductions of acetophenone, 3-chloropropiophenone, 4-hydroxyacetophenone, -tetralone, and 2-hydroxy-1-acetonapthone were investigated using NaBH4 as the reducing agent and a 10 mole % loading of the chiral catalysts. A stereoselectivity of 68% e.e. was obtained in the reduction of acetophenone, but attempts to reduce the selected imines to the corresponding chiral amines proved to be unsuccessful — even in the absence of the catalysts. It thus became apparent that the catalytic version of the reaction was not feasible.
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- Date Issued: 2016
Synthesis, characterization and electrochemistry of rhodium (iii) complexes of meso-substituted [14] tribenzotriphyrin (2.1. 1)
- Authors: Xue, Zhaoli , Wang, Yemei , Mack, John , Mkhize, Scebi , Nyokong, Tebello , Fang, Yuanyuan , Ou, Zhongping , Kadish, Karl M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241043 , vital:50899 , xlink:href="https://doi.org/10.1039/C6RA03028A"
- Description: A thermal reaction using a series of [14]tribenzotriphyrins(2.1.1) (TriPs, 1a–d) with Rh2(C8H12)Cl2 provides RhIII–TriP complexes (2a–d) in 40−52% yields. The complexes were characterized by mass spectrometry, UV-visible absorption and 1H NMR spectroscopy. Single crystal X-ray analysis reveals that 2b adopts a dome-shaped conformation. The rhodium(III) ion is coordinated by the three pyrrole nitrogen atoms, two chloride ions and the nitrogen atom of an acetonitrile (CH3CN) solvent molecule. The optical spectra can be assigned using Michl's perimeter model. The L and B bands of the 2a–d complexes lie at ca. 600 and 500 nm, respectively, and are markedly red shifted relative to those of 1a–d. A reversible one-electron oxidation and two reversible one-electron reductions are observed in the cyclic voltammograms of 2a–d in CH2Cl2. The redox potentials are consistent with the optical data and the relatively narrow HOMO–LUMO gaps that are predicted in DFT calculations. TD-DFT calculations have been used to assign a third intense spectral band at 375 nm to a higher energy π → π* transition of the [14]tribenzotriphyrin(2.1.1) π-system.
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- Date Issued: 2016
Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
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- Date Issued: 2016