Novel aspects of platinum-amine coordination compounds: their chemistry and anticancer application
- Authors: Bouwer, Yolanda
- Date: 2008
- Subjects: Coordination compounds , Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10444 , http://hdl.handle.net/10948/d1021052
- Description: The aim in this thesis, was to synthesize novel platinum coordination compounds, in order to develop compounds with improved anticancer action which could lead to an improved understanding of the mechanism by which they operate and at the same time, improve synthetic methods for their products. The initial work included the development of a novel synthetic method for 1R,2R-diaminocyclohexaneoxalato-platinum(II) (oxaliplatin), by using an essentially non-aqueous solvent medium and direct ligand exchange at elevated temperatures. This was done by a study of the kinetics of the reaction in a variety of conditions; such as relative reagent concentrations and ratios as well as solvent mixtures. An effective method was developed which could be applied industrially. An international patent was taken out on this method. Various amine complexes of platinum(II) were synthesized using chloro, bromo and oxalato groups as leaving groups. The non-leaving groups were selected having certain specific characteristics in mind. Novel mononitroplatinum(IV) complexes were synthesized, mostly with oxalato leaving groups. One of these in particular, had excellent anticancer behaviour. Another trichloromononitro complex was also synthesized with very good anticancer properties. Two international patents were filed for the latter two compounds. As far as possible, all compounds were studied by spectrometric, chromatographic and thermal methods. They were also tested against 3 cancer cell lines namely cervical (Hela), Colon (HT29) and Breast (MCF7) cancer cells.
- Full Text:
- Date Issued: 2008
- Authors: Bouwer, Yolanda
- Date: 2008
- Subjects: Coordination compounds , Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10444 , http://hdl.handle.net/10948/d1021052
- Description: The aim in this thesis, was to synthesize novel platinum coordination compounds, in order to develop compounds with improved anticancer action which could lead to an improved understanding of the mechanism by which they operate and at the same time, improve synthetic methods for their products. The initial work included the development of a novel synthetic method for 1R,2R-diaminocyclohexaneoxalato-platinum(II) (oxaliplatin), by using an essentially non-aqueous solvent medium and direct ligand exchange at elevated temperatures. This was done by a study of the kinetics of the reaction in a variety of conditions; such as relative reagent concentrations and ratios as well as solvent mixtures. An effective method was developed which could be applied industrially. An international patent was taken out on this method. Various amine complexes of platinum(II) were synthesized using chloro, bromo and oxalato groups as leaving groups. The non-leaving groups were selected having certain specific characteristics in mind. Novel mononitroplatinum(IV) complexes were synthesized, mostly with oxalato leaving groups. One of these in particular, had excellent anticancer behaviour. Another trichloromononitro complex was also synthesized with very good anticancer properties. Two international patents were filed for the latter two compounds. As far as possible, all compounds were studied by spectrometric, chromatographic and thermal methods. They were also tested against 3 cancer cell lines namely cervical (Hela), Colon (HT29) and Breast (MCF7) cancer cells.
- Full Text:
- Date Issued: 2008
Towards the bioremediation of the hypertrophic Swartkops Solar Salt-works
- Authors: Difford, Mark
- Date: 2008
- Subjects: Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10606 , http://hdl.handle.net/10948/1506 , Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Description: This thesis presents the results of three studies aimed at improving brine-quality at the Swartkops solar salt-works (Swartkops Sea Salt [Pty] Ltd) on the outskirts of Port Elizabeth, South Africa. This is a highly eutrophic salt-works, the management of which has become increasingly difficult in recent years. The fundamental problem is how best to operate the system at maximum capacity while limiting nutrient inputs from the nutrient-rich microtidal Swartkops Estuary. In the first study, brine-quality at several sites along the axis of the Swartkops Estuary, and the extent to which it is affected by a variety of factors, is compared. Sites were sampled on micro- and macrotidal time scales, and were selected by the management of the salt-works as possible locations for a new pump-house (for extracting brine from the estuary) for their salt-work operations at Swartkops and Missionvale. The study showed that there are incremental benefits to be had from moving the site of extraction downstream from its present position to a site closer to the mouth of the estuary, where the concentration of nutrients usually is lower and where salinity usually is higher. There is little to be gained from moving the site of extraction laterally, to the mouth of the Inlet from which brine currently is extracted, so that brine is extracted directly from the estuary itself. A set of models relating the concentrations of NH+ 4 , NO{u100000}3 , and PO34{u100000} to salinity is proposed. These take into account the influences of site and season and may be used to estimate the concentration of these nutrients from a measurement of salinity. The model for PO34{u100000} shows that it would be more damaging to the salt-works’ operations to pump “low”-salinity brine during the early months of summer than during autumn. Evidence is also presented to show that Wylde Bridge has no influence on nutrient concentrations in the estuary, with tidal flushing generally passing beyond the Wylde-Bridge break-point. The exceptionally heavy flooding of the estuary that occurred in September 2002 may, however, have biased this conclusion, because of its scouring effect. The second study concentrated on monitoring the effect of (1) decreasing pond depth and (2) increasing pond salinity—two readily available management tools—on brine quality at the salt-works. Pond depth throughout the salt-works was decreased by 40 cm, and the salinity of Pond 5, a pond in the middle of the system, was increased to 175 S. Both measures were kept in place for the duration of the study (Nov. 2002–Aug. 2004). The pond-depth experiment did not have the expected result, there being no evidence of the increase in microalgal growth in the water column that was predicted based on previous research. There was, however, a significant increase in benthic chlorophyll-a, and there was a general improvement in the condition of the sedimentary system of the salt-works. There was also a substantial decrease in particulate organic matter in the water column, with clear evidence that the remaining fraction was closely associated with living forms of particulate matter rather than with detritus. The pond-salinity experiment proves that there is a flourishing, and resilient, population of brine shrimp (Artemia salina L.) at the salt-works. Restocking the salina, or stocking it with a different strain of brine shrimp, is therefore not necessary. The results of this study show that the brine shrimp population at the salt-works needs salinities of greater than about 65–70 S to survive. As a living force they almost certainly need a protective salinity that is greater than about 120–140 S, perhaps even as great as 160 S. Brine shrimp thrived in the high salinity milieu of the experimental pond for the duration of the study, but dwindled from three other ponds of the system once their salinities fell to below 90 S, eventually to disappear from them, apparently completely, once salinity fell to below 65 S. The third and final study concentrated on establishing whether the products released by decomposing barley straw could be used in a solar salt-works to control macroalgal blooms without detrimentally affecting the benthic-mat. Previous research has shown that these products are effective inhibitors of macroalgal growth and that they remain effective under saline conditions. The results presented here show that the same products, or products released under similar conditions of decomposition, adversely effect both the structure and the function of the mat. Consequently, their use in a solar salt-works cannot be recommended.
- Full Text:
- Date Issued: 2008
- Authors: Difford, Mark
- Date: 2008
- Subjects: Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10606 , http://hdl.handle.net/10948/1506 , Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Description: This thesis presents the results of three studies aimed at improving brine-quality at the Swartkops solar salt-works (Swartkops Sea Salt [Pty] Ltd) on the outskirts of Port Elizabeth, South Africa. This is a highly eutrophic salt-works, the management of which has become increasingly difficult in recent years. The fundamental problem is how best to operate the system at maximum capacity while limiting nutrient inputs from the nutrient-rich microtidal Swartkops Estuary. In the first study, brine-quality at several sites along the axis of the Swartkops Estuary, and the extent to which it is affected by a variety of factors, is compared. Sites were sampled on micro- and macrotidal time scales, and were selected by the management of the salt-works as possible locations for a new pump-house (for extracting brine from the estuary) for their salt-work operations at Swartkops and Missionvale. The study showed that there are incremental benefits to be had from moving the site of extraction downstream from its present position to a site closer to the mouth of the estuary, where the concentration of nutrients usually is lower and where salinity usually is higher. There is little to be gained from moving the site of extraction laterally, to the mouth of the Inlet from which brine currently is extracted, so that brine is extracted directly from the estuary itself. A set of models relating the concentrations of NH+ 4 , NO{u100000}3 , and PO34{u100000} to salinity is proposed. These take into account the influences of site and season and may be used to estimate the concentration of these nutrients from a measurement of salinity. The model for PO34{u100000} shows that it would be more damaging to the salt-works’ operations to pump “low”-salinity brine during the early months of summer than during autumn. Evidence is also presented to show that Wylde Bridge has no influence on nutrient concentrations in the estuary, with tidal flushing generally passing beyond the Wylde-Bridge break-point. The exceptionally heavy flooding of the estuary that occurred in September 2002 may, however, have biased this conclusion, because of its scouring effect. The second study concentrated on monitoring the effect of (1) decreasing pond depth and (2) increasing pond salinity—two readily available management tools—on brine quality at the salt-works. Pond depth throughout the salt-works was decreased by 40 cm, and the salinity of Pond 5, a pond in the middle of the system, was increased to 175 S. Both measures were kept in place for the duration of the study (Nov. 2002–Aug. 2004). The pond-depth experiment did not have the expected result, there being no evidence of the increase in microalgal growth in the water column that was predicted based on previous research. There was, however, a significant increase in benthic chlorophyll-a, and there was a general improvement in the condition of the sedimentary system of the salt-works. There was also a substantial decrease in particulate organic matter in the water column, with clear evidence that the remaining fraction was closely associated with living forms of particulate matter rather than with detritus. The pond-salinity experiment proves that there is a flourishing, and resilient, population of brine shrimp (Artemia salina L.) at the salt-works. Restocking the salina, or stocking it with a different strain of brine shrimp, is therefore not necessary. The results of this study show that the brine shrimp population at the salt-works needs salinities of greater than about 65–70 S to survive. As a living force they almost certainly need a protective salinity that is greater than about 120–140 S, perhaps even as great as 160 S. Brine shrimp thrived in the high salinity milieu of the experimental pond for the duration of the study, but dwindled from three other ponds of the system once their salinities fell to below 90 S, eventually to disappear from them, apparently completely, once salinity fell to below 65 S. The third and final study concentrated on establishing whether the products released by decomposing barley straw could be used in a solar salt-works to control macroalgal blooms without detrimentally affecting the benthic-mat. Previous research has shown that these products are effective inhibitors of macroalgal growth and that they remain effective under saline conditions. The results presented here show that the same products, or products released under similar conditions of decomposition, adversely effect both the structure and the function of the mat. Consequently, their use in a solar salt-works cannot be recommended.
- Full Text:
- Date Issued: 2008
The solvent-free approach versus the use of ionic liquids in the synthesis of ferrocenes
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
Phytoplankton chlorophyll a concentration and community structure in two temporarily open/closed estuaries in the Eastern Cape, South Africa
- Authors: Gama, Phumelele Thuthuka
- Date: 2008
- Subjects: Estuarine ecology -- South Africa , Chlorophyll -- South Africa , Estuaries -- South Africa , Phytoplankton populations -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10621 , http://hdl.handle.net/10948/707 , Estuarine ecology -- South Africa , Chlorophyll -- South Africa , Estuaries -- South Africa , Phytoplankton populations -- South Africa
- Description: River flow is important in controlling phytoplankton distribution in estuaries. Data on the effect of river inflow on phytoplankton distribution patterns in temporarily open/closed estuaries is lacking. This study investigated the influence of river inflow on size-fractionated phytoplankton biomass (Chl a), community composition and environmental parameters measured monthly over three years in two temporarily open/closed estuaries in the Eastern Cape, South Africa. A once-off primary production study over an annual cycle was completed in the Van Stadens and Maitland estuaries. The study monitored physical, chemical and biological characteristics in both estuaries to examine the effects of changes in environmental factors and river inflow. Daily sampling of physico-chemical and biological variables from river to sea was carried out in the Van Stadens to investigate short-time scale effects of changes in environmental factors and river inflow on the phytoplankton biomass. Five and three stations in the main channel of the Van Stadens and Maitland estuaries respectively were sampled at 0.5 m below the water surface and 0.5 m above the sediment surface for biological and chemical variables and at the surface, 0.25 m and every 0.5 m thereafter for physical parameters. Five stations adjacent to the main channel along the estuary were monitored for groundwater macronutrient concentrations and five additional sites located within the upper catchment of the Van Stadens River were sampled on a quarterly basis over two years. Both estuaries were characterised by distinct hydrological conditions, an overwash, an open, a closed and a semi-closed mouth phase. Flooding in the Maitland and Van Stadens estuaries in 2001 and 2002 caused sediment scour, altered channel morphology and brought about breaching of the mouth. Flood driven mouth-breaching events occurred three and four times in each of the estuaries during the study. The mouth stayed open 20 – 25 percent and was closed 60 – 65 percent of the time. In the Van Stadens the closed overwash mouth condition occurred approximately 10 – 20 percent of the time while in the Maitland it occurred less with the semi-closed mouth condition occurring 10 – 20 percent of the time. Incidents related to mouth opening not associated with strong river floods occurred approximately 10 – 15 percent of the time, although in the Maitland a semi-closed mouth state persisted more frequently than in the Van Stadens Estuary. During flooding events salinity dropped to low levels (< 5 psu) but soon recovered to brackish conditions when river flow was reduced and marine water penetrated deep upstream. Reduction in river flow combined with marine sediment deposition resulted in the closure of the mouth. During closed mouth conditions strong onshore storm surges and spring high tides introduced marine water through overwash that kept salinity high. In both estuaries salinity showed a negative correlation with rainfall (R2 = 0.12), indicative of the strong influence of marine overwash that kept salinity high thus masking the influence of freshwater. High rainfall in the Van Stadens Estuary caused high levels of turbidity that reduced light penetration at depth. Light attenuation was positively correlated with the high rainfall (R 2 = 0.26) suggesting that increased turbidity was linked to rainfall induced discharge. In contrast, in the Maitland Estuary light attenuation did not show any correlation with increased rainfall possibly because of the reduced water depth and increased euphotic zone following the floods in 2002. High river inflow introduced macronutrients in both estuaries such that dissolved inorganic phosphates (DIP) and dissolved inorganic nitrogen (DIN) concentrations in the Van Stadens Estuary were strongly correlated with rainfall (R2 = 0.78 and 0.57 respectively). In the Maitland Estuary DIP and DIN concentrations remained significantly higher (p < 0.05) compared to that in the Van Stadens suggesting that the Maitland catchment contributed greater nutrient input into the estuary and may be associated with farming activities. Phytoplankton chlorophyll a (Chl a) ranged from 0.8 – 13.9 μg L-1 in the Van Stadens and in the Maitland Estuary from 5.3 – 138 μg L-1 during the 3-year study. During the open mouth condition Chl a biomass and primary production ranged from 5.4 – 52.9 μg Chl a L-1 and 1.2 – 11.7 mg C m-2 d-1 in the Maitland and in the Van Stadens from 1.6 – 9.8 μg Chl a L-1 and 1.2 - 14 mg C m-2 d-1 respectively. Maximum annual primary production in the Maitland and Van Stadens estuaries was 8.8 and 5.1 g C m-2 y-1 respectively. When the mouth was open in the Van Stadens Estuary the microphytoplankton (> 20 μm) accounted for > 65 percent of the Chl a, whereas during closed mouth conditions they accounted for about 55 percent of the Chl a biomass. Chlorophytes became the dominant taxon in the dry summer months but were replaced by cryptophytes and dinoflagellates during the wet season. When nutrient concentrations were low during low flow conditions in the Van Stadens Estuary mixotrophic microphytoplankton became an important fraction of the water column together with phototrophic dinoflagellates and cryptophytes. In the Maitland large sized chlorophytes were the dominant taxa in late spring and summer seasons and made up more than 80 percent of the cell numbers. In the Maitland before the floods in 2002 cyanophytes were the dominant group in late spring contributing more than 75 percent in cell abundance. Data from the short-term study in the Van Stadens Estuary showed similarities and differences in the Chl a response to increased river inflow. High river inflow initially reduced Chl a biomass followed by a recovery period of a couple of days compared to a 8 – 10 week recovery period in studies monitored over seasonal and annual temporal scales. The responses may be dissimilar but help to illustrate that there are similar response patterns to environmental forcing necessary to support phytoplankton biomass at different temporal scales. This study has demonstrated that flooding events caused by strong river flow cause breaching of the mouth, a reduction in salinity and marked nutrient input. Although the causes of flooding can be similar in both estuaries the resultant effects are varied and can alter the ability of the estuary to retain water. This study was able to demonstrate that the supply of macronutrients from the catchment was strongly correlated with rainfall (R2 = 0.67) and that phytoplankton growth mainly depended on an allochthonous source of macronutrients although internal supplies could be critical at times in controlling microalgal biomass.
- Full Text:
- Date Issued: 2008
- Authors: Gama, Phumelele Thuthuka
- Date: 2008
- Subjects: Estuarine ecology -- South Africa , Chlorophyll -- South Africa , Estuaries -- South Africa , Phytoplankton populations -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10621 , http://hdl.handle.net/10948/707 , Estuarine ecology -- South Africa , Chlorophyll -- South Africa , Estuaries -- South Africa , Phytoplankton populations -- South Africa
- Description: River flow is important in controlling phytoplankton distribution in estuaries. Data on the effect of river inflow on phytoplankton distribution patterns in temporarily open/closed estuaries is lacking. This study investigated the influence of river inflow on size-fractionated phytoplankton biomass (Chl a), community composition and environmental parameters measured monthly over three years in two temporarily open/closed estuaries in the Eastern Cape, South Africa. A once-off primary production study over an annual cycle was completed in the Van Stadens and Maitland estuaries. The study monitored physical, chemical and biological characteristics in both estuaries to examine the effects of changes in environmental factors and river inflow. Daily sampling of physico-chemical and biological variables from river to sea was carried out in the Van Stadens to investigate short-time scale effects of changes in environmental factors and river inflow on the phytoplankton biomass. Five and three stations in the main channel of the Van Stadens and Maitland estuaries respectively were sampled at 0.5 m below the water surface and 0.5 m above the sediment surface for biological and chemical variables and at the surface, 0.25 m and every 0.5 m thereafter for physical parameters. Five stations adjacent to the main channel along the estuary were monitored for groundwater macronutrient concentrations and five additional sites located within the upper catchment of the Van Stadens River were sampled on a quarterly basis over two years. Both estuaries were characterised by distinct hydrological conditions, an overwash, an open, a closed and a semi-closed mouth phase. Flooding in the Maitland and Van Stadens estuaries in 2001 and 2002 caused sediment scour, altered channel morphology and brought about breaching of the mouth. Flood driven mouth-breaching events occurred three and four times in each of the estuaries during the study. The mouth stayed open 20 – 25 percent and was closed 60 – 65 percent of the time. In the Van Stadens the closed overwash mouth condition occurred approximately 10 – 20 percent of the time while in the Maitland it occurred less with the semi-closed mouth condition occurring 10 – 20 percent of the time. Incidents related to mouth opening not associated with strong river floods occurred approximately 10 – 15 percent of the time, although in the Maitland a semi-closed mouth state persisted more frequently than in the Van Stadens Estuary. During flooding events salinity dropped to low levels (< 5 psu) but soon recovered to brackish conditions when river flow was reduced and marine water penetrated deep upstream. Reduction in river flow combined with marine sediment deposition resulted in the closure of the mouth. During closed mouth conditions strong onshore storm surges and spring high tides introduced marine water through overwash that kept salinity high. In both estuaries salinity showed a negative correlation with rainfall (R2 = 0.12), indicative of the strong influence of marine overwash that kept salinity high thus masking the influence of freshwater. High rainfall in the Van Stadens Estuary caused high levels of turbidity that reduced light penetration at depth. Light attenuation was positively correlated with the high rainfall (R 2 = 0.26) suggesting that increased turbidity was linked to rainfall induced discharge. In contrast, in the Maitland Estuary light attenuation did not show any correlation with increased rainfall possibly because of the reduced water depth and increased euphotic zone following the floods in 2002. High river inflow introduced macronutrients in both estuaries such that dissolved inorganic phosphates (DIP) and dissolved inorganic nitrogen (DIN) concentrations in the Van Stadens Estuary were strongly correlated with rainfall (R2 = 0.78 and 0.57 respectively). In the Maitland Estuary DIP and DIN concentrations remained significantly higher (p < 0.05) compared to that in the Van Stadens suggesting that the Maitland catchment contributed greater nutrient input into the estuary and may be associated with farming activities. Phytoplankton chlorophyll a (Chl a) ranged from 0.8 – 13.9 μg L-1 in the Van Stadens and in the Maitland Estuary from 5.3 – 138 μg L-1 during the 3-year study. During the open mouth condition Chl a biomass and primary production ranged from 5.4 – 52.9 μg Chl a L-1 and 1.2 – 11.7 mg C m-2 d-1 in the Maitland and in the Van Stadens from 1.6 – 9.8 μg Chl a L-1 and 1.2 - 14 mg C m-2 d-1 respectively. Maximum annual primary production in the Maitland and Van Stadens estuaries was 8.8 and 5.1 g C m-2 y-1 respectively. When the mouth was open in the Van Stadens Estuary the microphytoplankton (> 20 μm) accounted for > 65 percent of the Chl a, whereas during closed mouth conditions they accounted for about 55 percent of the Chl a biomass. Chlorophytes became the dominant taxon in the dry summer months but were replaced by cryptophytes and dinoflagellates during the wet season. When nutrient concentrations were low during low flow conditions in the Van Stadens Estuary mixotrophic microphytoplankton became an important fraction of the water column together with phototrophic dinoflagellates and cryptophytes. In the Maitland large sized chlorophytes were the dominant taxa in late spring and summer seasons and made up more than 80 percent of the cell numbers. In the Maitland before the floods in 2002 cyanophytes were the dominant group in late spring contributing more than 75 percent in cell abundance. Data from the short-term study in the Van Stadens Estuary showed similarities and differences in the Chl a response to increased river inflow. High river inflow initially reduced Chl a biomass followed by a recovery period of a couple of days compared to a 8 – 10 week recovery period in studies monitored over seasonal and annual temporal scales. The responses may be dissimilar but help to illustrate that there are similar response patterns to environmental forcing necessary to support phytoplankton biomass at different temporal scales. This study has demonstrated that flooding events caused by strong river flow cause breaching of the mouth, a reduction in salinity and marked nutrient input. Although the causes of flooding can be similar in both estuaries the resultant effects are varied and can alter the ability of the estuary to retain water. This study was able to demonstrate that the supply of macronutrients from the catchment was strongly correlated with rainfall (R2 = 0.67) and that phytoplankton growth mainly depended on an allochthonous source of macronutrients although internal supplies could be critical at times in controlling microalgal biomass.
- Full Text:
- Date Issued: 2008
On the optical characterization of photovoltaic devices
- Authors: Gxasheka, Andile Richman
- Date: 2008
- Subjects: Photovoltaic power systems -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10529 , http://hdl.handle.net/10948/692 , Photovoltaic power systems -- South Africa
- Description: Semiconductor materials used for making photovoltaic (PV) cells have defects and impurities due to constraints of keeping production costs low. Electrically active defects that are distributed over the bulk material lead to reduced overall performance of a photovoltaic (PV) cell. In this study an adaptable Light Beam Induced Current (LBIC) system was designed in order to characterize the local performance of PV cells. The system uses a laser source and objective lens mounted vertically above the sample on the X-Y stage. Two current pre-amplifiers are used for converting the photo-generated current from the PV cell and the signal from the reflection detector cell into a voltage that can be measured by the data acquisition board. Two configurations for measuring the photo-current maps of either bare cells or encapsulated PV mini-modules can be used. To add flexibility it was envisaged that the system would be built in such a way that it allows easy integration of carrier lifetime mapping capabilities while keeping costs to a minimum. The carrier lifetime measurement technique integrated into the LBIC system is based on the optical Open-Circuit Voltage-Decay (OCVD) method. In a single-crystalline silicon PV cell that was tested, photo-current and opencircuit voltage LBIC scans revealed shunting behaviour due to scratch marks on the front surface. The marks are believed to have been caused by poor handling during manufacturing process. Reduced photo-current due to edge shunting was observed towards the edges of the PV cell. In another sample of single crystalline silicon cell an edge shunt resulted in a 30 percent drop in photo-current measured. LBIC measurements performed on multi-crystalline cells revealed nonuniformities such as enhanced photo-current on one side of grain boundaries. These asymmetric enhancements of local photo-current are attributed to the incline of the grain boundary into the bulk of the material. LBIC results obtained from mini modules showed a high degree of mismatching from cell to cell. It is well known that mismatching can degrade the performance of a PV module with series connected cells. The LBIC measurements presented also illustrated the negative effects of delamination on the photo-current of PV modules. The LBIC measurements performed on mini PV modules highlight some of the benefits of using an LBIC technique as a tool for investigating PV cell’s local photo-current response. The effective lifetime maps obtained highlight the importance of optical OCVD method as a tool that can be used in conjunction with conventional LBIC technique. Effective minority carrier lifetimes around 40 ms were measured on a single crystalline silicon cell of 2.5 x 2.5 cm2. Local features such as cracks and lifetime degrading defects were revealed by LBIC maps and were also confirmed on effective lifetime maps. The results presented demonstrate the importance of using effective carrier lifetime maps to complement photocurrent maps of PV cells and identification of areas where defects are located.
- Full Text:
- Date Issued: 2008
- Authors: Gxasheka, Andile Richman
- Date: 2008
- Subjects: Photovoltaic power systems -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10529 , http://hdl.handle.net/10948/692 , Photovoltaic power systems -- South Africa
- Description: Semiconductor materials used for making photovoltaic (PV) cells have defects and impurities due to constraints of keeping production costs low. Electrically active defects that are distributed over the bulk material lead to reduced overall performance of a photovoltaic (PV) cell. In this study an adaptable Light Beam Induced Current (LBIC) system was designed in order to characterize the local performance of PV cells. The system uses a laser source and objective lens mounted vertically above the sample on the X-Y stage. Two current pre-amplifiers are used for converting the photo-generated current from the PV cell and the signal from the reflection detector cell into a voltage that can be measured by the data acquisition board. Two configurations for measuring the photo-current maps of either bare cells or encapsulated PV mini-modules can be used. To add flexibility it was envisaged that the system would be built in such a way that it allows easy integration of carrier lifetime mapping capabilities while keeping costs to a minimum. The carrier lifetime measurement technique integrated into the LBIC system is based on the optical Open-Circuit Voltage-Decay (OCVD) method. In a single-crystalline silicon PV cell that was tested, photo-current and opencircuit voltage LBIC scans revealed shunting behaviour due to scratch marks on the front surface. The marks are believed to have been caused by poor handling during manufacturing process. Reduced photo-current due to edge shunting was observed towards the edges of the PV cell. In another sample of single crystalline silicon cell an edge shunt resulted in a 30 percent drop in photo-current measured. LBIC measurements performed on multi-crystalline cells revealed nonuniformities such as enhanced photo-current on one side of grain boundaries. These asymmetric enhancements of local photo-current are attributed to the incline of the grain boundary into the bulk of the material. LBIC results obtained from mini modules showed a high degree of mismatching from cell to cell. It is well known that mismatching can degrade the performance of a PV module with series connected cells. The LBIC measurements presented also illustrated the negative effects of delamination on the photo-current of PV modules. The LBIC measurements performed on mini PV modules highlight some of the benefits of using an LBIC technique as a tool for investigating PV cell’s local photo-current response. The effective lifetime maps obtained highlight the importance of optical OCVD method as a tool that can be used in conjunction with conventional LBIC technique. Effective minority carrier lifetimes around 40 ms were measured on a single crystalline silicon cell of 2.5 x 2.5 cm2. Local features such as cracks and lifetime degrading defects were revealed by LBIC maps and were also confirmed on effective lifetime maps. The results presented demonstrate the importance of using effective carrier lifetime maps to complement photocurrent maps of PV cells and identification of areas where defects are located.
- Full Text:
- Date Issued: 2008
The separation of platinum and gold from an industrial feed solution
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
Novel camphor derivatives as potential asymmetric alkylation auxiliaries
- Authors: Skiti-Mama, Neliswa
- Date: 2008
- Subjects: Alkylation , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10372 , http://hdl.handle.net/10948/1077 , Alkylation , Chemistry, Organic
- Description: The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.
- Full Text:
- Date Issued: 2008
- Authors: Skiti-Mama, Neliswa
- Date: 2008
- Subjects: Alkylation , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10372 , http://hdl.handle.net/10948/1077 , Alkylation , Chemistry, Organic
- Description: The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.
- Full Text:
- Date Issued: 2008
Identification and characterization of novel oncology related platinum complexes using chromatographic and mass spectrometric techniques
- Authors: Wentzel, Mauritz
- Date: 2008
- Subjects: Chromatographic analysis , Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10310 , http://hdl.handle.net/10948/715 , Chromatographic analysis , Spectrum analysis
- Description: In this thesis mass spectral and chromatographic techniques were developed and applied to identify and characterise numerous novel platinum(II) and (IV) compounds designed as anticancer agents. In a novel method for the synthesis of cis-oxalato(trans- -1,2- cyclohexanediamine)platinum(II) or oxaliplatin these techniques could be applied to differentiate between the molecular complex and the autoionised analogue (viz. Ptdach2 2+Ptox2 2-). In another novel synthetic method for the same compound the ligand exchange reactions at various temperatures could be investigated and kinetic curves obtained served to illuminate the chemistry involved, indicating the role of small amounts of water in the essentially non-aqueous solvent systems dmf and isoamyl alcohol respectively. These allowed ligand exchange without resulting in hydrolyses even up to 85°C. The ionisation rate of divalent platinum halide complexes was determined for various amine ligands as well as N-S chelate ligands. A comparison of these could suggest why N-S complexes have poor anticancer action. Ionisation was not only studied for neutral molecular species but also for monocationic ones. Relationships could be found with stereochemical aspects of the chelates used. By investigating results of EV-CAD studies thermodynamic data could be obtained which indicated that bond strength decreases from chloro to iodo analogues although extent of ionisation in aqueous solution, i.e kinetic stability, is the reverse. Products formed by the reaction of NO2 gas with Platinum(II) compounds could be identified and separated which greatly contributed to the understanding of the chemistry involved in the formation of mononitro platinum(IV) complexes. Some of these proved to have exceptional anticancer properties. Studies of the interaction of thiol containing biomolecules were performed as a function of time. The results contributed to the understanding of the action of the anticancer agents.
- Full Text:
- Date Issued: 2008
- Authors: Wentzel, Mauritz
- Date: 2008
- Subjects: Chromatographic analysis , Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10310 , http://hdl.handle.net/10948/715 , Chromatographic analysis , Spectrum analysis
- Description: In this thesis mass spectral and chromatographic techniques were developed and applied to identify and characterise numerous novel platinum(II) and (IV) compounds designed as anticancer agents. In a novel method for the synthesis of cis-oxalato(trans- -1,2- cyclohexanediamine)platinum(II) or oxaliplatin these techniques could be applied to differentiate between the molecular complex and the autoionised analogue (viz. Ptdach2 2+Ptox2 2-). In another novel synthetic method for the same compound the ligand exchange reactions at various temperatures could be investigated and kinetic curves obtained served to illuminate the chemistry involved, indicating the role of small amounts of water in the essentially non-aqueous solvent systems dmf and isoamyl alcohol respectively. These allowed ligand exchange without resulting in hydrolyses even up to 85°C. The ionisation rate of divalent platinum halide complexes was determined for various amine ligands as well as N-S chelate ligands. A comparison of these could suggest why N-S complexes have poor anticancer action. Ionisation was not only studied for neutral molecular species but also for monocationic ones. Relationships could be found with stereochemical aspects of the chelates used. By investigating results of EV-CAD studies thermodynamic data could be obtained which indicated that bond strength decreases from chloro to iodo analogues although extent of ionisation in aqueous solution, i.e kinetic stability, is the reverse. Products formed by the reaction of NO2 gas with Platinum(II) compounds could be identified and separated which greatly contributed to the understanding of the chemistry involved in the formation of mononitro platinum(IV) complexes. Some of these proved to have exceptional anticancer properties. Studies of the interaction of thiol containing biomolecules were performed as a function of time. The results contributed to the understanding of the action of the anticancer agents.
- Full Text:
- Date Issued: 2008
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