Synthesis, characterization and anticancer studies of Oxovanadium(iv) Dithiocarbamate complexes
- Authors: Hlobo, Priscilla Vuyiswa
- Date: 2019
- Subjects: Inorganic compounds -- Synthesis Chemistry, Inorganic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/19131 , vital:39880
- Description: Eight new oxovanadium(IV) dithiocarbamate complexes, formed by the interaction of vanadyl sulfate pentahydrate and as-synthesized dithiocarbamate ligands, potassium N-morpholine-4- dithiocarbamate ligand (L1), potassium N-piperidinedithiocarbamate (L2), potassium N-(4- methoxyphenyl)dithiocarbamate ligand (L3), potassium N-diallyldithiocarbamate ligand (L4), potassium N-phenyldithiocarbamate ligand (L5), potassium N-dibenzylminedithiocarbamate ligand (L6), potassium N-(4-methylphenyl)dithiocarbamate ligand (L7), N-(1Himidazoledithiocarbamate) fluoride ligand (L8) in aqueous ethanol are described. The resulting complexes were elemental analyses, molar conductance, infrared, electronic, and nuclear magnetic resonance spectral studies. The spectral studies confirmed the formation of the ligands and complexes. Four complexes [VO(L1)2], [VO(L3)2], [VO(L6)2], and [VO(L8)2] derived from potassium N-morpholine-4-dithiocarbamate ligand (L1), potassium N-(4- methoxyphenyl)dithiocarbamate ligand (L3), potassium N-dibenzylminedithiocarbamate ligand (L6), and N-(1H-imidazoledithiocarbamate) fluoride ligand (L8) were characterized using cyclic voltammetry, to study their electrochemical behavior. Square pyramid oxovanadium(IV) complexes were proposed with the metal ion coordinated to two bidentate dithiocarbamate ligands through sulphur to complete its square pyramidal geometry. The anticancer screening of four oxovanadium(IV) dithiocarbamate complexes [VO(L1)2], [VO(L3)2], [VO(L6)2], and [VO(L8)2] are described.
- Full Text:
- Date Issued: 2019
- Authors: Hlobo, Priscilla Vuyiswa
- Date: 2019
- Subjects: Inorganic compounds -- Synthesis Chemistry, Inorganic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/19131 , vital:39880
- Description: Eight new oxovanadium(IV) dithiocarbamate complexes, formed by the interaction of vanadyl sulfate pentahydrate and as-synthesized dithiocarbamate ligands, potassium N-morpholine-4- dithiocarbamate ligand (L1), potassium N-piperidinedithiocarbamate (L2), potassium N-(4- methoxyphenyl)dithiocarbamate ligand (L3), potassium N-diallyldithiocarbamate ligand (L4), potassium N-phenyldithiocarbamate ligand (L5), potassium N-dibenzylminedithiocarbamate ligand (L6), potassium N-(4-methylphenyl)dithiocarbamate ligand (L7), N-(1Himidazoledithiocarbamate) fluoride ligand (L8) in aqueous ethanol are described. The resulting complexes were elemental analyses, molar conductance, infrared, electronic, and nuclear magnetic resonance spectral studies. The spectral studies confirmed the formation of the ligands and complexes. Four complexes [VO(L1)2], [VO(L3)2], [VO(L6)2], and [VO(L8)2] derived from potassium N-morpholine-4-dithiocarbamate ligand (L1), potassium N-(4- methoxyphenyl)dithiocarbamate ligand (L3), potassium N-dibenzylminedithiocarbamate ligand (L6), and N-(1H-imidazoledithiocarbamate) fluoride ligand (L8) were characterized using cyclic voltammetry, to study their electrochemical behavior. Square pyramid oxovanadium(IV) complexes were proposed with the metal ion coordinated to two bidentate dithiocarbamate ligands through sulphur to complete its square pyramidal geometry. The anticancer screening of four oxovanadium(IV) dithiocarbamate complexes [VO(L1)2], [VO(L3)2], [VO(L6)2], and [VO(L8)2] are described.
- Full Text:
- Date Issued: 2019
Inhalable particulate systems for anti-tubercular drug delivery
- Nkanga, Christian Isalomboto
- Authors: Nkanga, Christian Isalomboto
- Date: 2017
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/37966 , vital:24720
- Description: Tuberculosis (TB) is a deadly infectious microbial disease that is currently dominating public health concerns. Among the pharmacological issues in the management of TB are the poor bioavailability of some anti-TB drugs, mostly due to the fast first-pass metabolism, and high drug load needed for combination therapy. These result in a lengthy treatment with several adverse effects causing decreased patient compliance. These factors often lead to the therapeutic failure and promote the development of drug resistant strains, justifying the urgent need for new therapeutic strategies. Liposomes are lipid-based particulate vehicles known to be the most clinically appointed drug carriers currently. Liposomal systems are reported to be rapidly engulfed by macrophages - where the mycobacterium often resides. This makes liposomes appropriate vehicles for targeted anti-TB drug delivery. Many research groups have reported the potential of liposomes systems to deliver anti-TB drugs. However, the costly formulation status of liposomes, due the use of expensive synthetic or highly purified natural phospholipids, is a limitation to the treatment of a poverty related infectious disease like TB. The aim of this study was to design and develop liposomes for pulmonary delivery of anti-TB drugs using crude soybean lecithin (CL) and its purirified version. CL is an FDA- approved naturally occurring phospholipid mixture that is quite cheap and readily available. Various liposome batches were prepared using a film hydration method and characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Liposomes composed of CL and cholesterol (Chol) in a 3:1 mass ratio were selected for drug encapsulation based on the following characteristics: polydispersity index (PDI, 0.28), mean particles sizes (PS, 502 nm) and zeta potential (ZP, -56 mV). Isoniazid (INH) was encapsulated as a model drug using a freeze-thaw loading technique and an HPLC method was validated for quantitative analysis. The physicochemical properties of INH-loaded liposomes were comprehensively investigated using thermal, microscopy and spectroscopic techniques. This formulation showed a high encapsulation efficiency (%EE) of 78%, much better than the liposomes made from purified lecithin, 20%. Other characteristics of INH- loaded liposomes, which make them attractive for pulmonary TB therapy, are presented in this dissertation. These include a controlled release of 50% of the encapsulated INH over 12 hours. Finally, rifampicin (RIF) was added as a hydrophobic model drug and several evaluations were conducted on these dual drug-loaded liposomes. Of particular interest, it was noted that the dual drug-loaded liposomes made of CL alone showed the highest %EE (59% for INH and 90% for RIF) compared to those containing Chol or those made of purified lecithin. Surprisingly, the average PS of the dual CL-based liposomes (1114 nm) was in the size range reported for optimum deep lung deposition and macrophage uptake. In addition, the mean ZP of these liposomes (-63 mV) seems to be favourable for their shelf stability and internalization by macrophages. Overall, these findings show that the dual CL-based liposomes developed would be promising for macrophage-targeting pulmonary delivery of anti-TB drugs.
- Full Text:
- Date Issued: 2017
- Authors: Nkanga, Christian Isalomboto
- Date: 2017
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/37966 , vital:24720
- Description: Tuberculosis (TB) is a deadly infectious microbial disease that is currently dominating public health concerns. Among the pharmacological issues in the management of TB are the poor bioavailability of some anti-TB drugs, mostly due to the fast first-pass metabolism, and high drug load needed for combination therapy. These result in a lengthy treatment with several adverse effects causing decreased patient compliance. These factors often lead to the therapeutic failure and promote the development of drug resistant strains, justifying the urgent need for new therapeutic strategies. Liposomes are lipid-based particulate vehicles known to be the most clinically appointed drug carriers currently. Liposomal systems are reported to be rapidly engulfed by macrophages - where the mycobacterium often resides. This makes liposomes appropriate vehicles for targeted anti-TB drug delivery. Many research groups have reported the potential of liposomes systems to deliver anti-TB drugs. However, the costly formulation status of liposomes, due the use of expensive synthetic or highly purified natural phospholipids, is a limitation to the treatment of a poverty related infectious disease like TB. The aim of this study was to design and develop liposomes for pulmonary delivery of anti-TB drugs using crude soybean lecithin (CL) and its purirified version. CL is an FDA- approved naturally occurring phospholipid mixture that is quite cheap and readily available. Various liposome batches were prepared using a film hydration method and characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Liposomes composed of CL and cholesterol (Chol) in a 3:1 mass ratio were selected for drug encapsulation based on the following characteristics: polydispersity index (PDI, 0.28), mean particles sizes (PS, 502 nm) and zeta potential (ZP, -56 mV). Isoniazid (INH) was encapsulated as a model drug using a freeze-thaw loading technique and an HPLC method was validated for quantitative analysis. The physicochemical properties of INH-loaded liposomes were comprehensively investigated using thermal, microscopy and spectroscopic techniques. This formulation showed a high encapsulation efficiency (%EE) of 78%, much better than the liposomes made from purified lecithin, 20%. Other characteristics of INH- loaded liposomes, which make them attractive for pulmonary TB therapy, are presented in this dissertation. These include a controlled release of 50% of the encapsulated INH over 12 hours. Finally, rifampicin (RIF) was added as a hydrophobic model drug and several evaluations were conducted on these dual drug-loaded liposomes. Of particular interest, it was noted that the dual drug-loaded liposomes made of CL alone showed the highest %EE (59% for INH and 90% for RIF) compared to those containing Chol or those made of purified lecithin. Surprisingly, the average PS of the dual CL-based liposomes (1114 nm) was in the size range reported for optimum deep lung deposition and macrophage uptake. In addition, the mean ZP of these liposomes (-63 mV) seems to be favourable for their shelf stability and internalization by macrophages. Overall, these findings show that the dual CL-based liposomes developed would be promising for macrophage-targeting pulmonary delivery of anti-TB drugs.
- Full Text:
- Date Issued: 2017
Fatty acid composition, colour stability and lipid oxidation of mince produced from fresh and frozen/thawed fallow deer meat
- Authors: Chido, Chakanya
- Date: 2016
- Subjects: Lipids -- Oxidation Meat -- Preservation Mincemeat
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/2479 , vital:27874
- Description: The aim of the study was to determine the fatty acid composition, colour stability and lipid oxidation of fresh mince produced from fallow deer and to evaluate the effect of frozen storage duration on the retail display shelf life of the mince. A total of 31 fallow deer carcasses were used in the study. After cooling for 24hrs, the carcasses were deboned, external fat from the fore and hindquarter muscles removed and individually vacuum packed. For the first trial, seven fallow deer carcasses were used. Meat from the hind and fore-quarters of each carcass was divided into two equal batches per animal. One batch was minced (through a 5 mm die) and packed into oxygen permeable overwraps and refrigerated at 4°C for a period of eight days under retail display conditions. The second batch was vacuum packed and frozen at -20°C for 2 months at the end of which mince was also produced and monitored over an eight-day period under the same conditions that were used for the fresh mince. Colour, pH, lipid and myoglobin stability was determined. Proximate and fatty acid composition was also determined. No differences (P>0.05) were noted between proximate composition of fresh and frozen/thawed minced meat. The lipid content of fallow deer was 2.4 percent (±0.04). Total n3 fatty acids differed (P<0.05) between treatments and decreased with increased storage and display day. There were significant (P<0.05) treatment and time interactions on all measured colour parameters, TBARS and myoglobin forms. Fresh mince was lighter and had higher redness (a*) and yellowness (b*) values than mince from two months frozen stored meat. Hue angle for fresh mince remained stable throughout display whereas it increased for frozen/thawed mince. Fresh mince had lower TBARS values than frozen/thawed mince. Minced meat produced from frozen/thawed deer meat had higher surface met-myoglobin and total met-myoglobin percentages. Surface and total oxy-myoglobin percentage was higher in fresh mince. The first trial clearly showed colour and lipid stability differences between fresh mince and mince from frozen/thawed meat. It also showed that fresh mince has a longer retail display life than mince produced from frozen/thawed meat (six days and four days, respectively). In the second trial, the effects of frozen storage duration on colour and lipid stability were investigated. Twenty-four fallow deer were used. Twelve were harvested in June (6male 6female) and the other twelve in August (6 male 6female) of the same year.Twenty four hours after harvesting, the fore and hindquarter muscles of the carcasses were deboned, vacuum packed and kept at -20°C until October (i.e. 2months and 4months frozen storage period). Upon thawing, the meat was processed into mince following the same procedure used for the first trialand displayed for a fiveday period under retail display conditions. Frozen duration and gender had no effect (P>0.05) on the proximate composition of fallow deer meat. The total amount of saturated fatty acids (SFA) increased and total amount of poly unsaturated fatty acids (PUFA) decreased as frozen duration and display day increased (P<0.05). Frozen duration affected (P<0.01) lipid oxidation and percentage oxy-myoglobin. Mince pH and all colour parameters (L*, a*, b*,hue and chroma) differed (P<0.05) between treatments on day zero and three. Display day was a significant factor (P<0.05) on all measured parameters. By day three all parameters except pH showed signs of extended oxidation and discolouration as evidenced by reduced redness, decreased colour intensity and high TBARS values. This study showed that prolonged frozen storage negatively affects the colour and lipid stability of meat and increases oxidation of PUFAs during frozen storage. However, the study also suggests that although frozen/thawed meat has a shorter retail display shelf life; the proximate composition of the meat remains unchanged.
- Full Text:
- Date Issued: 2016
- Authors: Chido, Chakanya
- Date: 2016
- Subjects: Lipids -- Oxidation Meat -- Preservation Mincemeat
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/2479 , vital:27874
- Description: The aim of the study was to determine the fatty acid composition, colour stability and lipid oxidation of fresh mince produced from fallow deer and to evaluate the effect of frozen storage duration on the retail display shelf life of the mince. A total of 31 fallow deer carcasses were used in the study. After cooling for 24hrs, the carcasses were deboned, external fat from the fore and hindquarter muscles removed and individually vacuum packed. For the first trial, seven fallow deer carcasses were used. Meat from the hind and fore-quarters of each carcass was divided into two equal batches per animal. One batch was minced (through a 5 mm die) and packed into oxygen permeable overwraps and refrigerated at 4°C for a period of eight days under retail display conditions. The second batch was vacuum packed and frozen at -20°C for 2 months at the end of which mince was also produced and monitored over an eight-day period under the same conditions that were used for the fresh mince. Colour, pH, lipid and myoglobin stability was determined. Proximate and fatty acid composition was also determined. No differences (P>0.05) were noted between proximate composition of fresh and frozen/thawed minced meat. The lipid content of fallow deer was 2.4 percent (±0.04). Total n3 fatty acids differed (P<0.05) between treatments and decreased with increased storage and display day. There were significant (P<0.05) treatment and time interactions on all measured colour parameters, TBARS and myoglobin forms. Fresh mince was lighter and had higher redness (a*) and yellowness (b*) values than mince from two months frozen stored meat. Hue angle for fresh mince remained stable throughout display whereas it increased for frozen/thawed mince. Fresh mince had lower TBARS values than frozen/thawed mince. Minced meat produced from frozen/thawed deer meat had higher surface met-myoglobin and total met-myoglobin percentages. Surface and total oxy-myoglobin percentage was higher in fresh mince. The first trial clearly showed colour and lipid stability differences between fresh mince and mince from frozen/thawed meat. It also showed that fresh mince has a longer retail display life than mince produced from frozen/thawed meat (six days and four days, respectively). In the second trial, the effects of frozen storage duration on colour and lipid stability were investigated. Twenty-four fallow deer were used. Twelve were harvested in June (6male 6female) and the other twelve in August (6 male 6female) of the same year.Twenty four hours after harvesting, the fore and hindquarter muscles of the carcasses were deboned, vacuum packed and kept at -20°C until October (i.e. 2months and 4months frozen storage period). Upon thawing, the meat was processed into mince following the same procedure used for the first trialand displayed for a fiveday period under retail display conditions. Frozen duration and gender had no effect (P>0.05) on the proximate composition of fallow deer meat. The total amount of saturated fatty acids (SFA) increased and total amount of poly unsaturated fatty acids (PUFA) decreased as frozen duration and display day increased (P<0.05). Frozen duration affected (P<0.01) lipid oxidation and percentage oxy-myoglobin. Mince pH and all colour parameters (L*, a*, b*,hue and chroma) differed (P<0.05) between treatments on day zero and three. Display day was a significant factor (P<0.05) on all measured parameters. By day three all parameters except pH showed signs of extended oxidation and discolouration as evidenced by reduced redness, decreased colour intensity and high TBARS values. This study showed that prolonged frozen storage negatively affects the colour and lipid stability of meat and increases oxidation of PUFAs during frozen storage. However, the study also suggests that although frozen/thawed meat has a shorter retail display shelf life; the proximate composition of the meat remains unchanged.
- Full Text:
- Date Issued: 2016
Mesopredator release and the effectiveness of camera traps for estimating mammal abundances in the Eastern Cape, South Africa
- Authors: Taylor, Jonathan Michael
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3587 , vital:20527
- Description: Remotely operated cameras (camera traps) have become an indispensable tool for many ecologists, particularly those studying rare and elusive animals. A plethora of camera trap makes and models are now commercially available, yet the effects of their varying design features on the quality and quantity of data recorded remains principally unknown. Better understanding of differing camera trap designs is needed before adequate management policies can be implemented, especially when the aim is to protect vulnerable and endangered species such as many carnivores. Habitat loss and human conflict has prompted worldwide declines of apex predator populations. Following this, many smaller predators have undergone population ‘explosions’ due to the lack of top-down forcing, a phenomenon known as mesopredator release. Land use changes in the Eastern Cape of South Africa have caused extensive degradation and fragmentation of the Subtropical Thicket Biome. In addition, coupled with anthropogenic persecution, apex predators including lions (Panthera leo), leopards (P. pardus), and brown hyaenas (Hyaena brunnea) have been extirpated from large areas of their historic range. Removal of these apex predators may provide opportunity for mesopredators, such as black-backed jackals (Canis mesomelas) and caracals (Caracal caracal), to be released from top-down forcing and possibly initiate trophic cascade effects. Therefore, using randomly distributed camera traps, my study aimed to explore the quality and quantity of data collected by different camera trap designs, and to investigate the mesopredator release hypothesis in the Eastern Cape of South Africa. A total of 2,989 trap nights was used to compare camera trap designs. Camera traps with narrow detection zones and fast trigger speeds (≤ 0.25 seconds) recorded a higher diversity of carnivores, but there was no significant difference in the relative abundances of carnivore species recorded by different camera trap models. A total of 19,659 trap nights was used to assess mesopredator relative abundance, occupancy, distribution and daily activity patterns at one site with, and one site without, apex predators. Consistent with the mesopredator release hypothesis, black-backed jackal relative abundance was significantly higher in the absence of apex predators, and this was supported by occupancy analyses. Further, black-backed jackal distribution was significantly concentrated in areas where apex predator activity was low, possibly indicating spatial avoidance. There was no significant difference in caracal relative abundance, occupancy, distribution, or daily activity between sites. These results provide the first indication of mesopredator release of blackbacked jackals in the Eastern Cape. The implications of black-backed jackal release including prey population structure, local extinctions, altered seed dispersal and disease dynamics are discussed.
- Full Text:
- Date Issued: 2016
- Authors: Taylor, Jonathan Michael
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3587 , vital:20527
- Description: Remotely operated cameras (camera traps) have become an indispensable tool for many ecologists, particularly those studying rare and elusive animals. A plethora of camera trap makes and models are now commercially available, yet the effects of their varying design features on the quality and quantity of data recorded remains principally unknown. Better understanding of differing camera trap designs is needed before adequate management policies can be implemented, especially when the aim is to protect vulnerable and endangered species such as many carnivores. Habitat loss and human conflict has prompted worldwide declines of apex predator populations. Following this, many smaller predators have undergone population ‘explosions’ due to the lack of top-down forcing, a phenomenon known as mesopredator release. Land use changes in the Eastern Cape of South Africa have caused extensive degradation and fragmentation of the Subtropical Thicket Biome. In addition, coupled with anthropogenic persecution, apex predators including lions (Panthera leo), leopards (P. pardus), and brown hyaenas (Hyaena brunnea) have been extirpated from large areas of their historic range. Removal of these apex predators may provide opportunity for mesopredators, such as black-backed jackals (Canis mesomelas) and caracals (Caracal caracal), to be released from top-down forcing and possibly initiate trophic cascade effects. Therefore, using randomly distributed camera traps, my study aimed to explore the quality and quantity of data collected by different camera trap designs, and to investigate the mesopredator release hypothesis in the Eastern Cape of South Africa. A total of 2,989 trap nights was used to compare camera trap designs. Camera traps with narrow detection zones and fast trigger speeds (≤ 0.25 seconds) recorded a higher diversity of carnivores, but there was no significant difference in the relative abundances of carnivore species recorded by different camera trap models. A total of 19,659 trap nights was used to assess mesopredator relative abundance, occupancy, distribution and daily activity patterns at one site with, and one site without, apex predators. Consistent with the mesopredator release hypothesis, black-backed jackal relative abundance was significantly higher in the absence of apex predators, and this was supported by occupancy analyses. Further, black-backed jackal distribution was significantly concentrated in areas where apex predator activity was low, possibly indicating spatial avoidance. There was no significant difference in caracal relative abundance, occupancy, distribution, or daily activity between sites. These results provide the first indication of mesopredator release of blackbacked jackals in the Eastern Cape. The implications of black-backed jackal release including prey population structure, local extinctions, altered seed dispersal and disease dynamics are discussed.
- Full Text:
- Date Issued: 2016
Study into the synthesis, characterisation and applications of Vanadium-based metal organic frameworks, using 1, 2, 4, 5-benzenetetracarboxylic acid
- Authors: Feldmann, Wesley
- Date: 2016
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/55245 , vital:26680
- Description: This study focussed on the synthesis, characterisation and catalytic application of synthesised vanadium-based Metal-Organic Frameworks using 1,2,4,5-benzenetetracarboxylic acid as a ligand. A number of synthetic methods were tested in multiple attempts to synthesise a V-MOF, these included; ambient, gel, reflux and solvothermal methods of synthesis. Two products of interest were identified, an ambient synthesis produced a vanadium-based complex with the empirical formula: V2O2(Na2H2B4C).6H2O (RU-V2) and a solvothermal synthesis produced a MOF with the empirical formula: V2O2(H2O)2(B4C) (RU-V1). Both products were characterised using elemental analysis, infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray powder diffraction. The catalytic activity of these products was tested, alongside the activity of the solid decavanadate ion, for the conversion of cyclohexene to cyclohexene oxide. The decavanadate ion was included to determine if the ion was catalytically active in the solid state, to potentially be used in the construction of a future MOF or V-complex. The reaction for the conversion of cyclohexene to cyclohexene oxide was chosen, as it has been previously conducted using a V-MOF and was found to be successful. The product of the reaction, the epoxide: cyclohexene oxide, is a very useful precursor for a number of reactions involved in the pharmaceutical industry, so developing catalysts which are able to convert cyclohexene to the epoxide with high yields and selectivities are well sought after in industry. The results of the catalytic reactions were varied, as the materials exhibited high yields and selectivities to the epoxide, but these results were only obtained when water was present in the reaction mixture. Water was able to bring about the cleavage of the bonds between the metal and ligand in a highly coordinated framework, at a faster rate than other solvents, such as decane. This ultimately leads to the structural decomposition of the entire complex or framework, depending upon the reaction time. The use of water was a double edged sword in that it was required to initiate the catalytic reaction, but was also the reason that the catalytic materials were noted to decompose over time. The solid decavanadate ion was only noted to exhibit homogeneous activity by dissolving into the small volume of water present in the reaction mixture. The study proved that using a multidentate ligand such as 1,2,4,5-benzenetetracarboxylic acid yielded products which were highly coordinated in nature and would therefore not have large open spaces associated with them, which is commonly observed with other MOFs. Instead the closed nature of the synthesised complexes and frameworks offered a different environment for catalytic reactions, where the small pores/channels had a controlling and inhibiting effect on the reaction. The conversion of cyclohexene to the epoxide is accompanied with a number of undesired side products, so when using the synthesised closed-natured MOF, it was found that there was a greater selectivity for the epoxide over other potential products. This indicates that close natured MOFs may find application in catalytic reactions which require high selectivities for a particular product.
- Full Text:
- Date Issued: 2016
- Authors: Feldmann, Wesley
- Date: 2016
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/55245 , vital:26680
- Description: This study focussed on the synthesis, characterisation and catalytic application of synthesised vanadium-based Metal-Organic Frameworks using 1,2,4,5-benzenetetracarboxylic acid as a ligand. A number of synthetic methods were tested in multiple attempts to synthesise a V-MOF, these included; ambient, gel, reflux and solvothermal methods of synthesis. Two products of interest were identified, an ambient synthesis produced a vanadium-based complex with the empirical formula: V2O2(Na2H2B4C).6H2O (RU-V2) and a solvothermal synthesis produced a MOF with the empirical formula: V2O2(H2O)2(B4C) (RU-V1). Both products were characterised using elemental analysis, infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray powder diffraction. The catalytic activity of these products was tested, alongside the activity of the solid decavanadate ion, for the conversion of cyclohexene to cyclohexene oxide. The decavanadate ion was included to determine if the ion was catalytically active in the solid state, to potentially be used in the construction of a future MOF or V-complex. The reaction for the conversion of cyclohexene to cyclohexene oxide was chosen, as it has been previously conducted using a V-MOF and was found to be successful. The product of the reaction, the epoxide: cyclohexene oxide, is a very useful precursor for a number of reactions involved in the pharmaceutical industry, so developing catalysts which are able to convert cyclohexene to the epoxide with high yields and selectivities are well sought after in industry. The results of the catalytic reactions were varied, as the materials exhibited high yields and selectivities to the epoxide, but these results were only obtained when water was present in the reaction mixture. Water was able to bring about the cleavage of the bonds between the metal and ligand in a highly coordinated framework, at a faster rate than other solvents, such as decane. This ultimately leads to the structural decomposition of the entire complex or framework, depending upon the reaction time. The use of water was a double edged sword in that it was required to initiate the catalytic reaction, but was also the reason that the catalytic materials were noted to decompose over time. The solid decavanadate ion was only noted to exhibit homogeneous activity by dissolving into the small volume of water present in the reaction mixture. The study proved that using a multidentate ligand such as 1,2,4,5-benzenetetracarboxylic acid yielded products which were highly coordinated in nature and would therefore not have large open spaces associated with them, which is commonly observed with other MOFs. Instead the closed nature of the synthesised complexes and frameworks offered a different environment for catalytic reactions, where the small pores/channels had a controlling and inhibiting effect on the reaction. The conversion of cyclohexene to the epoxide is accompanied with a number of undesired side products, so when using the synthesised closed-natured MOF, it was found that there was a greater selectivity for the epoxide over other potential products. This indicates that close natured MOFs may find application in catalytic reactions which require high selectivities for a particular product.
- Full Text:
- Date Issued: 2016
The contribution of smallholder agriculture production to food security in rural Zimbabwe : a case study of Masvingo Province
- Authors: Toringepi, Godfrey
- Date: 2016
- Subjects: Farms, Small -- Zimbabwe Agricultural productivity -- Zimbabwe Sustainable agriculture -- Zimbabwe
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/5598 , vital:29350
- Description: Agricultural development is back on the development agenda. Even though the smallholder farmers are in the majority and at the forefront in terms of food production and agriculture being the backbone of the economy of Zimbabwe, there is no clearly defined policy on smallholder agriculture in Zimbabwe. The food insecurity has remained a continuous challenge for the rural poor in Zimbabwe. This study investigated the contribution of smallholder agriculture to food security with particular reference to the Masvingo province. The study employed qualitative method of research entailing extensive review of literature as a method of data collection. The study utilized the modernisation theory and sustainable livelihoods framework to illustrate smallholder agriculture and food security nexus. The study revealed that smallholder agriculture is the best option for addressing food security since agriculture is considered the main livelihood strategy for small scale farmers in Zimbabwe. There is general scholarly consensus that the main cause of food insecurity in Zimbabwe is a decrease in smallholder agriculture productivity. The study revealed that poor infrastructure , limited access to credit, limited access to inputs, poor investment in human development, limited access to markets and harsh climatic conditions weaken the capacity of small scale farmers to improve food security. Key recommendations are that supportive institutions need to be put in place to strengthen the smallholder farmer’s capacity to improve food security in Zimbabwe.
- Full Text:
- Date Issued: 2016
- Authors: Toringepi, Godfrey
- Date: 2016
- Subjects: Farms, Small -- Zimbabwe Agricultural productivity -- Zimbabwe Sustainable agriculture -- Zimbabwe
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/5598 , vital:29350
- Description: Agricultural development is back on the development agenda. Even though the smallholder farmers are in the majority and at the forefront in terms of food production and agriculture being the backbone of the economy of Zimbabwe, there is no clearly defined policy on smallholder agriculture in Zimbabwe. The food insecurity has remained a continuous challenge for the rural poor in Zimbabwe. This study investigated the contribution of smallholder agriculture to food security with particular reference to the Masvingo province. The study employed qualitative method of research entailing extensive review of literature as a method of data collection. The study utilized the modernisation theory and sustainable livelihoods framework to illustrate smallholder agriculture and food security nexus. The study revealed that smallholder agriculture is the best option for addressing food security since agriculture is considered the main livelihood strategy for small scale farmers in Zimbabwe. There is general scholarly consensus that the main cause of food insecurity in Zimbabwe is a decrease in smallholder agriculture productivity. The study revealed that poor infrastructure , limited access to credit, limited access to inputs, poor investment in human development, limited access to markets and harsh climatic conditions weaken the capacity of small scale farmers to improve food security. Key recommendations are that supportive institutions need to be put in place to strengthen the smallholder farmer’s capacity to improve food security in Zimbabwe.
- Full Text:
- Date Issued: 2016
The effect of grain and soya bean-based diets on chicken production, some egg quality traits, and the potential for allergen carryover to eggs and meat
- Authors: Dokora, Adia-En-Michelle
- Date: 2015
- Subjects: Chickens -- Nutrition Chickens --Feeding and feeds Meat -- Quality
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/2946 , vital:28192
- Description: This study determined the effect of maize-, whole wheat-, soya bean-based-diets on the growth performance, egg quality and dressing percentage of chickens, as well as the potential for soy and gluten allergen carryover to eggs and meat from chickens. Twenty 36-week-old Lorham White (LW) hens were divided into two groups and kept in individual cages until they reached 39-weeks of age, with water and feed supplied ad libitum. Ten LW hens were fed a maize/soya bean-based diet (T1) and the other ten birds were fed a maize/soya bean-based diet with a 15 percent whole wheat inclusion (T2) for a period of four weeks, with weekly individual hen weights and group feed consumption figures being recorded. After a two-week diet adaptation period, six eggs per treatment group were collected every second day from the LW hens’ to measure egg quality traits. Every third day, over a 29-day period, six eggs per treatment were collected and analysed for the presence of soy, gluten and gluten-derived peptides using allergen specific enzyme linked immunosorbent assays (ELISA) kits. For the broiler trial, a total of 160 Ross 308 mixed sex day old chicks were used in a completely randomized design. Two dietary treatments were assigned to eight cages (replicate) per treatment, with ten birds per cage. The Ross 308 broiler feeding programme consisted of three phases, starter (day 1 to day 10), grower (day 11 to day 20) and finisher (day 21 to day 28). At the beginning of the trial all chicks were fed T1 which contained a maize/soya bean-based diet for a period of 10 days and then eight cages with 10 birds per cage were randomly selected and fed the T2 diet, which contained a maize/soya bean-based diet with a 15 percent whole wheat inclusion, until they reached 28 days of age. Weekly live weights, feed intake, average daily gain and the average daily feed intake were recorded and calculated. At the end of the grower (day 21) and finisher phase (day 28), one broiler bird was selected per cage to have eight (8) birds per treatment and 16 birds per phase that were slaughtered and breast meat samples were analysed in duplicate for the presence of soy and gluten allergens using ELISA kits. The dressing percentage of hot carcasses was also determined at the end of the finisher phase on eight birds per treatment. For LW hens, live weight (LW) at 39 weeks of age, the average daily feed intake (ADFI) and weekly feed intakes (FI) were significantly different (P < 0.05) between treatments with birds on T2 recording higher gains. As birds age in weeks increased, significant differences (P < 0.05) in live weight values were recorded. Egg quality traits measured (shell weight, yolk weight, albumen weight, albumen height and Haugh units) were significantly different (P < 0.05) between treatments, with eggs from hens receiving T1 recording higher mean values. As hens got older, the colour of egg yolk improved, producing eggs with higher b* (yellowness) values and lower L* (lightness) and a* (redness) mean values. The Haugh unit, significantly improved (P < 0.05) as the hens got older, signifying better quality of eggs. For the broiler birds, growth traits measured indicated that there were no significant differences (P > 0.05) in live weight (LW), average daily feed intake (ADFI), weekly feed intake (FI), feed conversion ratio (FCR), cumulative feed intake (CFI) and cumulative gain (CG) between treatments. No significant differences (P > 0.05) between dressing percentage of broilers from the two treatments were observed. As birds grew, significant differences (P < 0.05) in LW, FI, AFI, FCR, and CFI, over a four-week period were recorded. Results of the allergen analyses indicated that soy and gluten allergens were not carried over from feed into eggs and meat of chickens fed a maize/soya bean-based diet and a maize/soya bean-based with a 15 percent whole wheat inclusion, respectively. In conclusion, a maize/soya bean-based diet and maize/soya bean-based diet with a 15 percent whole wheat inclusion that contained soy and gluten allergens, are feed sources that promote and stimulate 36-week-old LW hen and Ross 308 chicken growth.
- Full Text:
- Date Issued: 2015
- Authors: Dokora, Adia-En-Michelle
- Date: 2015
- Subjects: Chickens -- Nutrition Chickens --Feeding and feeds Meat -- Quality
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10353/2946 , vital:28192
- Description: This study determined the effect of maize-, whole wheat-, soya bean-based-diets on the growth performance, egg quality and dressing percentage of chickens, as well as the potential for soy and gluten allergen carryover to eggs and meat from chickens. Twenty 36-week-old Lorham White (LW) hens were divided into two groups and kept in individual cages until they reached 39-weeks of age, with water and feed supplied ad libitum. Ten LW hens were fed a maize/soya bean-based diet (T1) and the other ten birds were fed a maize/soya bean-based diet with a 15 percent whole wheat inclusion (T2) for a period of four weeks, with weekly individual hen weights and group feed consumption figures being recorded. After a two-week diet adaptation period, six eggs per treatment group were collected every second day from the LW hens’ to measure egg quality traits. Every third day, over a 29-day period, six eggs per treatment were collected and analysed for the presence of soy, gluten and gluten-derived peptides using allergen specific enzyme linked immunosorbent assays (ELISA) kits. For the broiler trial, a total of 160 Ross 308 mixed sex day old chicks were used in a completely randomized design. Two dietary treatments were assigned to eight cages (replicate) per treatment, with ten birds per cage. The Ross 308 broiler feeding programme consisted of three phases, starter (day 1 to day 10), grower (day 11 to day 20) and finisher (day 21 to day 28). At the beginning of the trial all chicks were fed T1 which contained a maize/soya bean-based diet for a period of 10 days and then eight cages with 10 birds per cage were randomly selected and fed the T2 diet, which contained a maize/soya bean-based diet with a 15 percent whole wheat inclusion, until they reached 28 days of age. Weekly live weights, feed intake, average daily gain and the average daily feed intake were recorded and calculated. At the end of the grower (day 21) and finisher phase (day 28), one broiler bird was selected per cage to have eight (8) birds per treatment and 16 birds per phase that were slaughtered and breast meat samples were analysed in duplicate for the presence of soy and gluten allergens using ELISA kits. The dressing percentage of hot carcasses was also determined at the end of the finisher phase on eight birds per treatment. For LW hens, live weight (LW) at 39 weeks of age, the average daily feed intake (ADFI) and weekly feed intakes (FI) were significantly different (P < 0.05) between treatments with birds on T2 recording higher gains. As birds age in weeks increased, significant differences (P < 0.05) in live weight values were recorded. Egg quality traits measured (shell weight, yolk weight, albumen weight, albumen height and Haugh units) were significantly different (P < 0.05) between treatments, with eggs from hens receiving T1 recording higher mean values. As hens got older, the colour of egg yolk improved, producing eggs with higher b* (yellowness) values and lower L* (lightness) and a* (redness) mean values. The Haugh unit, significantly improved (P < 0.05) as the hens got older, signifying better quality of eggs. For the broiler birds, growth traits measured indicated that there were no significant differences (P > 0.05) in live weight (LW), average daily feed intake (ADFI), weekly feed intake (FI), feed conversion ratio (FCR), cumulative feed intake (CFI) and cumulative gain (CG) between treatments. No significant differences (P > 0.05) between dressing percentage of broilers from the two treatments were observed. As birds grew, significant differences (P < 0.05) in LW, FI, AFI, FCR, and CFI, over a four-week period were recorded. Results of the allergen analyses indicated that soy and gluten allergens were not carried over from feed into eggs and meat of chickens fed a maize/soya bean-based diet and a maize/soya bean-based with a 15 percent whole wheat inclusion, respectively. In conclusion, a maize/soya bean-based diet and maize/soya bean-based diet with a 15 percent whole wheat inclusion that contained soy and gluten allergens, are feed sources that promote and stimulate 36-week-old LW hen and Ross 308 chicken growth.
- Full Text:
- Date Issued: 2015
Characterization and application of phthalocyanine-magnetic nanoparticle conjugates anchored to electrospun polyamide nanofibers
- Authors: Ledwaba, Mpho
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54610 , vital:26593
- Description: This work presents the syntheses, photophysical and photochemical characterization of zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc, 3) and its gadolinium oxide nanoparticle conjugate (4). By means of spectroscopic and microscopic characterization, the conjugation of the ZnTCPPc to the silica coated gadolinium oxide nanoparticles (Si-Gd2O3 NPs, 2) through an amide bond was confirmed. The thermal stability, morphology, nanoparticle sizes and their conjugates with the Pc were studied using ThermoGravimetric Analysis (TGA), Fourier Transform Infrared spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and powder X-ray diffractometry (XRD). Conjugation of ZnTCPPc to the magnetic nanoparticles, proved to have a negligible effect on the photophysical parameters of the phthalocyanine, where a slight decrease in fluorescence and triplet quantum yields and lifetimes was observed. The singlet oxygen quantum yield, however, increased slightly upon conjugation, suggesting that the overall efficiency of the ZnTCPPc as a photosensitizer had improved. Physical mixing of the ZnTCPPc and the silica-coated gadolinium nanoparticles also showed an improvement in the singlet oxygen quantum yield and triplet lifetime, also showing an enhanced efficiency for the photosensitizer and therefore photocatalysis. ZnTCPPc (3) alone and the Pc-gadolinium oxide nanoparticle conjugate (4) were therefore electrospun into nanofibers to create a solid support. The fibers were characterized and their diameter sizes and composition was studied confirming the incorporation of the phthalocyanine and gadolinium oxide nanoparticle. Increased singlet oxygen generation resulted in increased Photodegradation of the environmental pollutant Orange G and the fibers were found to be more efficient as photocatalysts compared to the photosensitizer in solution. The nanomaterial may therefore be applied to the photodegradation of Orange G.
- Full Text:
- Date Issued: 2014
- Authors: Ledwaba, Mpho
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54610 , vital:26593
- Description: This work presents the syntheses, photophysical and photochemical characterization of zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc, 3) and its gadolinium oxide nanoparticle conjugate (4). By means of spectroscopic and microscopic characterization, the conjugation of the ZnTCPPc to the silica coated gadolinium oxide nanoparticles (Si-Gd2O3 NPs, 2) through an amide bond was confirmed. The thermal stability, morphology, nanoparticle sizes and their conjugates with the Pc were studied using ThermoGravimetric Analysis (TGA), Fourier Transform Infrared spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and powder X-ray diffractometry (XRD). Conjugation of ZnTCPPc to the magnetic nanoparticles, proved to have a negligible effect on the photophysical parameters of the phthalocyanine, where a slight decrease in fluorescence and triplet quantum yields and lifetimes was observed. The singlet oxygen quantum yield, however, increased slightly upon conjugation, suggesting that the overall efficiency of the ZnTCPPc as a photosensitizer had improved. Physical mixing of the ZnTCPPc and the silica-coated gadolinium nanoparticles also showed an improvement in the singlet oxygen quantum yield and triplet lifetime, also showing an enhanced efficiency for the photosensitizer and therefore photocatalysis. ZnTCPPc (3) alone and the Pc-gadolinium oxide nanoparticle conjugate (4) were therefore electrospun into nanofibers to create a solid support. The fibers were characterized and their diameter sizes and composition was studied confirming the incorporation of the phthalocyanine and gadolinium oxide nanoparticle. Increased singlet oxygen generation resulted in increased Photodegradation of the environmental pollutant Orange G and the fibers were found to be more efficient as photocatalysts compared to the photosensitizer in solution. The nanomaterial may therefore be applied to the photodegradation of Orange G.
- Full Text:
- Date Issued: 2014
Distribution of iron-titanium oxides in the vanadiferous main magnetite seam of the upper zone : Northern limb, Bushveld complex
- Authors: Gwatinetsa, Demand
- Date: 2014
- Subjects: Igneous rocks -- South Africa -- Bushveld Complex , Sulfide minerals -- South Africa -- Bushveld Complex , Vanadium -- South Africa -- Bushveld Complex , Titanium dioxide -- South Africa -- Bushveld Complex , Ferric oxide -- South Africa -- Bushveld Complex , Geology -- South Africa -- Bushveld Complex , Mineralogy -- South Africa -- Bushveld Complex , Mines and mineral resources -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5063 , http://hdl.handle.net/10962/d1013281
- Description: The main magnetite seam of the Upper Zone of the Rustenburg Layered Suite (SACS, 1980) on the Bushveld Complex is known to host the world‘s largest vanadium bearing titaniferous iron ores. The vanadiferous titanomagnetites, contain vanadium in sufficient concentrations (1.2 - 2.2 per cent V₂O₅) to be considered as resources and vanadium has been mined historically by a number of companies among them Anglo-American, Highveld Steel and Vanadium and VanMag Resources as well as currently by Evraz Highveld Steel and Vanadium Limited of South Africa. The titanomagnetites contain iron ore in the form of magnetite and titanium with concentrations averaging 50-75 per cent FeO and 12-21 per cent TiO₂. The titaniferous iron ores have been historically dismissed as a source of iron and titanium, due to the known difficulties of using iron ore with high titania content in blast furnaces. The economic potential for the extractability of the titaniferous magnetites lies in the capacity of the ores to be separated into iron rich and titanium rich concentrates usually through, crushing, grinding and magnetic separation. The separatability of iron oxides and titanium oxides, is dependent on the nature in which the titanium oxide occurs, with granular ilmenite being the most favourable since it can be separated from magnetite via magnetic separation. Titanium that occurs as finely exsolved lamellae or as iron-titanium oxides with low titania content such as ulvospinel render the potential recoverability of titanium poor. The Upper Zone vanadiferous titanomagnetites contain titanium in various forms varying from discrete granular ilmenite to finely exsolved lamellae as well as occurring as part of the minerals ulvospinel (Fe₂TiO₄) and titanomagnetite (a solid solution series between ulvospinel and magnetite) . Discrete ilmenite constitutes between 3-5 per cent by volume of the massive titanomagnetite ores, and between 5-10 per cent by volume of the magnetite-plagioclase cumulates with more than 50 per cent opaque oxide minerals. The purpose of this research was to investigate the mineralogical setting and distribution of the iron and titanium oxides within the magnetitite layers from top to bottom as well as spatially along a strike length of 2 000m to determine the potential for the titanium to be extracted from the titanomagnetite ores. The titanomagnetites of the Upper Zone of the Bushveld Complex with particular reference to the Northern Limb where this research was conducted contains titanium oxides as discrete ilmenite grains but in low concentrations whose potential for separate economic extraction will be challenging. The highest concentration of titanium in the magnetite ores is not contained in the granular ilmenite, but rather in ulvospinel and titanomagnetite as illustrated by the marked higher concentration of TiO₂ in the massive ores which contain less granular ilmenite in comparison to the disseminated ores which contain 3 to 8 percentage points higher granular ilmenite than the massive ores. On the scale of the main magnetite seam, the TiO₂ content increases with increasing stratigraphic height from being completely absent in the footwall anorthosite. The V₂2O₅ content also increases with stratigraphic height except for in one of the 3 boreholes where it drops with increasing height. The decrease or increase patterns are repeated in every seam. The titanomagnetites of the main magnetite seam display a variety of textures from coarse granular magnetite and ilmenite, to trellis ilmenite lamellae, intergranular ilmenite and magnesian spinels and fine exsolution lamellae of ulvospinel and ferro-magnesian spinels parallel to the magnetite cleavage. The bottom contact of the main magnetite seam is very sharp and there is no titanium or vanadium in the footwall barely 10cm below the contact. Chromium is present in the bottom of the 4 layers that constitute the main magnetite seam and it upwards decreases rapidly. In boreholes P21 and P55, there are slight reversals in the TiO₂ and V₂O₅ content towards the top of the magnetite seams.
- Full Text:
- Date Issued: 2014
- Authors: Gwatinetsa, Demand
- Date: 2014
- Subjects: Igneous rocks -- South Africa -- Bushveld Complex , Sulfide minerals -- South Africa -- Bushveld Complex , Vanadium -- South Africa -- Bushveld Complex , Titanium dioxide -- South Africa -- Bushveld Complex , Ferric oxide -- South Africa -- Bushveld Complex , Geology -- South Africa -- Bushveld Complex , Mineralogy -- South Africa -- Bushveld Complex , Mines and mineral resources -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5063 , http://hdl.handle.net/10962/d1013281
- Description: The main magnetite seam of the Upper Zone of the Rustenburg Layered Suite (SACS, 1980) on the Bushveld Complex is known to host the world‘s largest vanadium bearing titaniferous iron ores. The vanadiferous titanomagnetites, contain vanadium in sufficient concentrations (1.2 - 2.2 per cent V₂O₅) to be considered as resources and vanadium has been mined historically by a number of companies among them Anglo-American, Highveld Steel and Vanadium and VanMag Resources as well as currently by Evraz Highveld Steel and Vanadium Limited of South Africa. The titanomagnetites contain iron ore in the form of magnetite and titanium with concentrations averaging 50-75 per cent FeO and 12-21 per cent TiO₂. The titaniferous iron ores have been historically dismissed as a source of iron and titanium, due to the known difficulties of using iron ore with high titania content in blast furnaces. The economic potential for the extractability of the titaniferous magnetites lies in the capacity of the ores to be separated into iron rich and titanium rich concentrates usually through, crushing, grinding and magnetic separation. The separatability of iron oxides and titanium oxides, is dependent on the nature in which the titanium oxide occurs, with granular ilmenite being the most favourable since it can be separated from magnetite via magnetic separation. Titanium that occurs as finely exsolved lamellae or as iron-titanium oxides with low titania content such as ulvospinel render the potential recoverability of titanium poor. The Upper Zone vanadiferous titanomagnetites contain titanium in various forms varying from discrete granular ilmenite to finely exsolved lamellae as well as occurring as part of the minerals ulvospinel (Fe₂TiO₄) and titanomagnetite (a solid solution series between ulvospinel and magnetite) . Discrete ilmenite constitutes between 3-5 per cent by volume of the massive titanomagnetite ores, and between 5-10 per cent by volume of the magnetite-plagioclase cumulates with more than 50 per cent opaque oxide minerals. The purpose of this research was to investigate the mineralogical setting and distribution of the iron and titanium oxides within the magnetitite layers from top to bottom as well as spatially along a strike length of 2 000m to determine the potential for the titanium to be extracted from the titanomagnetite ores. The titanomagnetites of the Upper Zone of the Bushveld Complex with particular reference to the Northern Limb where this research was conducted contains titanium oxides as discrete ilmenite grains but in low concentrations whose potential for separate economic extraction will be challenging. The highest concentration of titanium in the magnetite ores is not contained in the granular ilmenite, but rather in ulvospinel and titanomagnetite as illustrated by the marked higher concentration of TiO₂ in the massive ores which contain less granular ilmenite in comparison to the disseminated ores which contain 3 to 8 percentage points higher granular ilmenite than the massive ores. On the scale of the main magnetite seam, the TiO₂ content increases with increasing stratigraphic height from being completely absent in the footwall anorthosite. The V₂2O₅ content also increases with stratigraphic height except for in one of the 3 boreholes where it drops with increasing height. The decrease or increase patterns are repeated in every seam. The titanomagnetites of the main magnetite seam display a variety of textures from coarse granular magnetite and ilmenite, to trellis ilmenite lamellae, intergranular ilmenite and magnesian spinels and fine exsolution lamellae of ulvospinel and ferro-magnesian spinels parallel to the magnetite cleavage. The bottom contact of the main magnetite seam is very sharp and there is no titanium or vanadium in the footwall barely 10cm below the contact. Chromium is present in the bottom of the 4 layers that constitute the main magnetite seam and it upwards decreases rapidly. In boreholes P21 and P55, there are slight reversals in the TiO₂ and V₂O₅ content towards the top of the magnetite seams.
- Full Text:
- Date Issued: 2014
Synthesis and characterization of NaYGdF4 upconversion nanoparticles and an investigation of their effects on the spectroscopic properties of two phthalocyanine dyes
- Authors: Taylor, Jessica Mary
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54621 , vital:26594
- Description: Sphere and star shaped NaYGdF4:Yb/Er(Tm) upconversion nanoparticles were successfully synthesized utilizing a methanol assisted thermal decomposition approach and their chemical, spectroscopic and fluorescence properties were fully characterized. In addition, their influence on the spectroscopic and fluorescence properties of two phthalocyanines (Pcs) (unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) and aluminium octacarboxy phthalocyanine (Cl)AlOCPc) was investigated. Upconversion nanoparticles were found to produce characteristic upconversion fluorescence emissions in the blue, green, red and NIR regions and were also shown to possess paramagnetic properties. Simple mixing with an H2Pc in toluene was found to exert no change on the spectroscopic or fluorescence properties of the Pc while covalent conjugation to a (Cl)AlOCPc resulted in a large Q band blue shift accompanied by a decrease in fluorescence lifetimes in DMSO. The red light excitation mediated singlet oxygen generation of the H2Pc mixed with upconversion nanoparticles was investigated and singlet oxygen fluorescence lifetimes were found to decrease in the presence of the nanoparticles. Upconversion mediated singlet oxygen generation, by way of resonance energy transfer to the Pc, was also attempted using 972 nm excitation; however, no singlet oxygen was detected utilizing singlet oxygen NIR emission detection. Pending further work using alternative singlet oxygen detection methods, this suggests that while upconversion nanoparticles possess excellent fluorescent imaging capabilities, they are relatively inefficient in inducing singlet oxygen production simply when mixed with phthalocyanines. Despite this, by combining phthalocyanines and upconversion nanoparticles, we present a system capable of: multimodal imaging, using both upconversion and phthalocyanines emissions, singlet oxygen generation, via direct excitation of the phthalocyanine with red laser light, and, possibly, magnetic resonance imaging, as a result of doping the upconversion nanoparticles with Gd3+ ions.
- Full Text:
- Date Issued: 2014
- Authors: Taylor, Jessica Mary
- Date: 2014
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/54621 , vital:26594
- Description: Sphere and star shaped NaYGdF4:Yb/Er(Tm) upconversion nanoparticles were successfully synthesized utilizing a methanol assisted thermal decomposition approach and their chemical, spectroscopic and fluorescence properties were fully characterized. In addition, their influence on the spectroscopic and fluorescence properties of two phthalocyanines (Pcs) (unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) and aluminium octacarboxy phthalocyanine (Cl)AlOCPc) was investigated. Upconversion nanoparticles were found to produce characteristic upconversion fluorescence emissions in the blue, green, red and NIR regions and were also shown to possess paramagnetic properties. Simple mixing with an H2Pc in toluene was found to exert no change on the spectroscopic or fluorescence properties of the Pc while covalent conjugation to a (Cl)AlOCPc resulted in a large Q band blue shift accompanied by a decrease in fluorescence lifetimes in DMSO. The red light excitation mediated singlet oxygen generation of the H2Pc mixed with upconversion nanoparticles was investigated and singlet oxygen fluorescence lifetimes were found to decrease in the presence of the nanoparticles. Upconversion mediated singlet oxygen generation, by way of resonance energy transfer to the Pc, was also attempted using 972 nm excitation; however, no singlet oxygen was detected utilizing singlet oxygen NIR emission detection. Pending further work using alternative singlet oxygen detection methods, this suggests that while upconversion nanoparticles possess excellent fluorescent imaging capabilities, they are relatively inefficient in inducing singlet oxygen production simply when mixed with phthalocyanines. Despite this, by combining phthalocyanines and upconversion nanoparticles, we present a system capable of: multimodal imaging, using both upconversion and phthalocyanines emissions, singlet oxygen generation, via direct excitation of the phthalocyanine with red laser light, and, possibly, magnetic resonance imaging, as a result of doping the upconversion nanoparticles with Gd3+ ions.
- Full Text:
- Date Issued: 2014
The nature and origin of gold mineralization in the Tugela valley, Natal Structural and Metamorphic Province
- Authors: De Klerk, Ian Duncan
- Date: 1991
- Subjects: Gold ores -- Geology -- South Africa , Gold mines and mining -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4979 , http://hdl.handle.net/10962/d1005591 , Gold ores -- Geology -- South Africa , Gold mines and mining -- South Africa
- Description: The project area is situated within the Tugela Valley, located in the Northern Marginal Zone of the Natal Structural and Metamorphic Province, and this work outlines the different styles of gold mineralization found in the Tugela Valley. Two different styles have been recognized and both have economic significance:- 1) Epigenetic shear zone-hosted gold occurs in late-stage relatively undeformed thin quartz veins confined to shear zones, and is present in both the greenschist facies Natal Thrust Belt and the amphibolite facies Natal Nappe Complex. However the vast majority of these occurrences are concentrated within the thrust front (i.e. the Natal Thrust Belt). The gold grades (up to 7 g/t) and the hydrothermal alteration assemblages associated with the epigenetic deposits have been documented. 2) An as yet unrecognized occurrence of syngenetic gold mineralization is found associated with the sediment-hosted exhalative massive, to semi-massive, sulphides of the iThuma prospect, located within the amphibolite facies Natal Nappe Complex. Here gold (up to 3 g/t) is concentrated together with the main sulphide are, as well as some gold enrichment (230ppb) in the hydrothermally altered footwall feeder pipe. It is proposed that the epigenetic mineralization was formed as a consequence of the northward directed abduction of the major thrust slices of the Natal Nappe Complex. This increased the permeability of the rocks and provided channelways for the focussing of fluids. Deposition took place at the thrust front where metamorphic hydrothermal fluids interacted with meteoric water.
- Full Text:
- Date Issued: 1991
- Authors: De Klerk, Ian Duncan
- Date: 1991
- Subjects: Gold ores -- Geology -- South Africa , Gold mines and mining -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4979 , http://hdl.handle.net/10962/d1005591 , Gold ores -- Geology -- South Africa , Gold mines and mining -- South Africa
- Description: The project area is situated within the Tugela Valley, located in the Northern Marginal Zone of the Natal Structural and Metamorphic Province, and this work outlines the different styles of gold mineralization found in the Tugela Valley. Two different styles have been recognized and both have economic significance:- 1) Epigenetic shear zone-hosted gold occurs in late-stage relatively undeformed thin quartz veins confined to shear zones, and is present in both the greenschist facies Natal Thrust Belt and the amphibolite facies Natal Nappe Complex. However the vast majority of these occurrences are concentrated within the thrust front (i.e. the Natal Thrust Belt). The gold grades (up to 7 g/t) and the hydrothermal alteration assemblages associated with the epigenetic deposits have been documented. 2) An as yet unrecognized occurrence of syngenetic gold mineralization is found associated with the sediment-hosted exhalative massive, to semi-massive, sulphides of the iThuma prospect, located within the amphibolite facies Natal Nappe Complex. Here gold (up to 3 g/t) is concentrated together with the main sulphide are, as well as some gold enrichment (230ppb) in the hydrothermally altered footwall feeder pipe. It is proposed that the epigenetic mineralization was formed as a consequence of the northward directed abduction of the major thrust slices of the Natal Nappe Complex. This increased the permeability of the rocks and provided channelways for the focussing of fluids. Deposition took place at the thrust front where metamorphic hydrothermal fluids interacted with meteoric water.
- Full Text:
- Date Issued: 1991
Gold metallogeny of Australia
- Authors: Rankine, Graham M
- Date: 1987
- Subjects: Gold ores -- Geology -- Australia , Gold mines and mining -- Australia , Gold -- Metallurgy -- Australia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4928 , http://hdl.handle.net/10962/d1004676
- Description: The gold metallogeny of Australia is predominantly confined to the Archaean and Palaeozoic Provinces. The Archaean gold occurrences are predominantly hosted in ultramafic-mafic dominated greenstone belts, with less associated tofelsic-volcanic and sedimentary sequences. Most gold occurrences are confined to shear zones or faults, and adjacent discoveries of economic laterite-hosted deposits, host rocks. Recent are presently under investigation and will supply a significant proportion of production in the future. The Proterozoic gold deposits of Australia , are confined to geosyncinal sequences, commonly turbidites (eg: Telfer), with other hydrothermal deposits associated directly to granites. An important feature of the North Australian Craton deposits, is the spatial association of most deposits to granite bodies, although a genetic link has not been established conclusively. The Roxby Downs deposit in South Australia is a unique occurrence of gold in association to copper, uranium and R.E.E. This deposit is tentatively related to intraplate alkaline-magmatism, with further work necessary. The most significant recent discovery of gold mineralization in Australia is in the Drummond Basin in Queensland. This epithermal is tentatively related to mineralization within the Georgetown Inlier. The latter mineralization is Permo-Carboniferous, in a Proterozoic (and possibly Archaean) sequence of schists. It is tentatively suggested that all the gold mineralization in northern Queensland may be related to single tectonic event, a feature which requires further study . Other mineralization in the Phanerozoic includes the turbidite-hosted metamorphogenic deposits of Victoria, the rift related deposits in New South Wales and magmatic related deposits in Queensland. The gold deposits in Australia may in the future be classified in a tectonogeological framework, similiar to the layout of this dissertation, particularly once further data becomes available on recent discoveries.
- Full Text:
- Date Issued: 1987
- Authors: Rankine, Graham M
- Date: 1987
- Subjects: Gold ores -- Geology -- Australia , Gold mines and mining -- Australia , Gold -- Metallurgy -- Australia
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4928 , http://hdl.handle.net/10962/d1004676
- Description: The gold metallogeny of Australia is predominantly confined to the Archaean and Palaeozoic Provinces. The Archaean gold occurrences are predominantly hosted in ultramafic-mafic dominated greenstone belts, with less associated tofelsic-volcanic and sedimentary sequences. Most gold occurrences are confined to shear zones or faults, and adjacent discoveries of economic laterite-hosted deposits, host rocks. Recent are presently under investigation and will supply a significant proportion of production in the future. The Proterozoic gold deposits of Australia , are confined to geosyncinal sequences, commonly turbidites (eg: Telfer), with other hydrothermal deposits associated directly to granites. An important feature of the North Australian Craton deposits, is the spatial association of most deposits to granite bodies, although a genetic link has not been established conclusively. The Roxby Downs deposit in South Australia is a unique occurrence of gold in association to copper, uranium and R.E.E. This deposit is tentatively related to intraplate alkaline-magmatism, with further work necessary. The most significant recent discovery of gold mineralization in Australia is in the Drummond Basin in Queensland. This epithermal is tentatively related to mineralization within the Georgetown Inlier. The latter mineralization is Permo-Carboniferous, in a Proterozoic (and possibly Archaean) sequence of schists. It is tentatively suggested that all the gold mineralization in northern Queensland may be related to single tectonic event, a feature which requires further study . Other mineralization in the Phanerozoic includes the turbidite-hosted metamorphogenic deposits of Victoria, the rift related deposits in New South Wales and magmatic related deposits in Queensland. The gold deposits in Australia may in the future be classified in a tectonogeological framework, similiar to the layout of this dissertation, particularly once further data becomes available on recent discoveries.
- Full Text:
- Date Issued: 1987
Geochemical and mineralogical aspects of the Molteno Formation, South Africa
- Authors: Reynolds, Adrian J
- Date: 1980
- Subjects: Sediments (Geology) -- South Africa , Mineralogy -- South Africa , Petrology -- South Africa , Geochemistry -- South Africa , Molteno Formation (South Africa)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4901 , http://hdl.handle.net/10962/d1001561
- Description: The Triassic Molteno Formation is a clastic sedimentary sequence consisting of a series of cycles, dominated lithologically by coarse grained sandstones. Aspects of the petrography have been examined using the conventional petrographic microscope as well as the scanning electron microscope. Both solution and overgrowth features are present not only on the quartz grains but also on certain of the heavy mineral species present. Intrastratal solution of garnet would appear to be a significant feature in the Molteno Formation. Mineralogical examination of the laterally persistent Indwe Sandstone Member indicates no significant variation in heavy mineral content. Evidence from a study of zircon elongation ratios shows the presence of two distinct zircon populations indicating two provenance areas. X-ray diffraction and electron microprobe analysis has identified mineral species characteristic of granites, pegmatitic granite and metamorphic rocks, especially amphibolites. Palaeocurrent data indicates that this source area lay to the south-east; to the south the source area consisted mainly of the Cape Supergroup sediments. Analysis for Nb, Zr, Y, Sr, Rb, Zn, Mn, Ba, Cu, Ni, Co, Cr, V and Ti for 22 samples from the Molteno Formation, indicates, as expected for a highly arenaceous sequence, a substantial depletion in these trace elements. No consistent variation of trace element concentration occurs with height in the sequence so trace element content may not be used for purposes of stratigraphic correlation. There are indications of trace element variation with geographical position, no doubt a reflection of the contribution of 2 source areas of different compositions. Factor analysis of the interelement correlations has identified 3 factors which influence the trace element content of the Molteno Formation these are a "heavy mineral" factor, a "pH-Eh" factor and a "clay mineral" factor. These trace factors are ultimately an expression of the source rock composition, the prevailing climate and a combination of the two. Comparison with the more argillaceous overlying Elliot Formation, indicates that factors influencing geochemical variation in this sequence were far more complex than for the Molteno Formation
- Full Text:
- Date Issued: 1980
- Authors: Reynolds, Adrian J
- Date: 1980
- Subjects: Sediments (Geology) -- South Africa , Mineralogy -- South Africa , Petrology -- South Africa , Geochemistry -- South Africa , Molteno Formation (South Africa)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4901 , http://hdl.handle.net/10962/d1001561
- Description: The Triassic Molteno Formation is a clastic sedimentary sequence consisting of a series of cycles, dominated lithologically by coarse grained sandstones. Aspects of the petrography have been examined using the conventional petrographic microscope as well as the scanning electron microscope. Both solution and overgrowth features are present not only on the quartz grains but also on certain of the heavy mineral species present. Intrastratal solution of garnet would appear to be a significant feature in the Molteno Formation. Mineralogical examination of the laterally persistent Indwe Sandstone Member indicates no significant variation in heavy mineral content. Evidence from a study of zircon elongation ratios shows the presence of two distinct zircon populations indicating two provenance areas. X-ray diffraction and electron microprobe analysis has identified mineral species characteristic of granites, pegmatitic granite and metamorphic rocks, especially amphibolites. Palaeocurrent data indicates that this source area lay to the south-east; to the south the source area consisted mainly of the Cape Supergroup sediments. Analysis for Nb, Zr, Y, Sr, Rb, Zn, Mn, Ba, Cu, Ni, Co, Cr, V and Ti for 22 samples from the Molteno Formation, indicates, as expected for a highly arenaceous sequence, a substantial depletion in these trace elements. No consistent variation of trace element concentration occurs with height in the sequence so trace element content may not be used for purposes of stratigraphic correlation. There are indications of trace element variation with geographical position, no doubt a reflection of the contribution of 2 source areas of different compositions. Factor analysis of the interelement correlations has identified 3 factors which influence the trace element content of the Molteno Formation these are a "heavy mineral" factor, a "pH-Eh" factor and a "clay mineral" factor. These trace factors are ultimately an expression of the source rock composition, the prevailing climate and a combination of the two. Comparison with the more argillaceous overlying Elliot Formation, indicates that factors influencing geochemical variation in this sequence were far more complex than for the Molteno Formation
- Full Text:
- Date Issued: 1980
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