Removal and recovery of gold and platinum from aqueous solutions utilising the non-viable biomass Asolla filiculoides
- Authors: Antunes, Ana Paula Martins
- Date: 2002
- Subjects: Azolla filiculoides Metal wastes -- Recycling Gold -- Recycling Platinum -- Recycling
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3894 , http://hdl.handle.net/10962/d1003726
- Description: Waste water from the mining industry is generally extremely complex and contains numerous species which influence the adsorption of the metals to any biomass. A variety of factors need to be addressed before treatment is considered viable. It is also beneficial to establish the binding characteristics of the metal of interest to maximise its interaction with the biomass to be utilised. Azalia filiculaides was investigated in the adsorption of gold(III), lead(II), iron(ID), copper(II) and platinum (IV). In batch studies, the optimum biomass and initial gold(III) concentrations were found to be 5 gIL and 8 mgIL respectively. The adsorption of gold(ID) is principally pH-dependent with optimal removal at pH 2. Lead(II), iron(III) and copper(II) did not compete with gold(III) adsorption under equimolar and simulated effluent conditions. Halides, with increasing affinity for gold (chloride < bromide < iodide), can affect gold uptake with the soft base, iodide, exhibiting the most inhibition (25%) and the hard base, chloride, O%. Mercaptoethanol (soft base) showed no interference in gold(III) adsorption while the presence of sulphate (hard base) and sulphite (borderline base) showed that concentrations in excess of 1 0 mM may adversely affect gold(ill) uptake, most likely due to competition for cationic sites on the biomass. Column studies, better suited to high volume treatment, indicated that a flow-rate of 5 mL/min and an initial gold(ill) concentration of 5 mgIL was optimal. Competitive effects between lead, iron, copper and gold again showed little or no interference. The halides, chloride, bromide and iodide, affect gold(ill) uptake similarly to the batch studies, while the bases mercaptoethanol and sulphate minimally affect gold(III) binding with sulphite severely hampering adsorption (70% inhibition). To optimise gold desorption, preliminary batch studies indicated that a ratio of 1:1 of adsorbentdesorbent was optimal, whilst gas purging of thiourea with oxygen, air and nitrogen decreased gold elution in proportion to decreased amounts of oxygen. A series of desorbents were utilised, in column studies, to optimise and determine the speciation of bound gold. The presence of an oxidant with thiourea enhanced desorption greater than 3 fold when compared with thiourea alone. Thiourea desorption studies, aided by the oxidant, suggest that gold is present in the + I and 0 oxidation states. Ultimately thiourea, perchloric acid and hydrochloric acid was found to be the most optimal elutant for gold (J 00% recovery). For selective metal recovery oflead and copper, pre-washing the plant material with water, utilising an acid (0.3 M nitric acid), pumping in an up-flow mode, and recycling the desorbent six times was found to be optimal elutant for gold (J 00% recovery). Cost analysis of utilising elutant versus incinerating the biomass for gold recovery indicated the latter as the most economical. Over a 5 cycle adsorption and desorption series, acid desorption before each adsorption cycle was found to result in greater than 92% desorption for lead and 96% for copper. Gold recovery was 97% with incineration. A preliminary study with gold effluent (Mine C) indicated that nickel and sulphate was removed in batch and column studies. Gold removal was found to be 100% and 4% in batch and column studies respectively. Adsorption of gold in the effluent study was accompanied by the release ofHt. Modifying the plant material with various reagents failed to identify the primary binding sites and the role of polysaccharides, proteins and lipids in gold(ill) uptake. The mode of gold binding is suggested as being initially ionic, this is very rapid, with the interaction of the anionic complex, [AuCI₄]". with the cationic biomass (PH 2). This eventually leads to the displacement of the chloride ligand(s) initiating covalent binding. Spectral studies of the chemical interaction between gold and the representative tannins indicated the protonated hydroxy groups to be responsible. All evidence suggests that the binding mechanisms of gold are not simple. Preliminary adsorption studies of platinum by Azalia filiculaides were conducted. Batch studies indicated that J gIL biomass concentration, initial platinum concentration of 20 mgIL and pH 2 are optimal, while the column studies indicated a flow-rate of! 0 rnL/min and initial platinum concentration of 20 mgIL as optimal. In the platinum effluent study, platinum showed a removal of 23 % and 2 J % for the batch and column studies respectively. Again adsorption was accompanied by //' release. Azalia filiculaides demonstrated its feasibility in the removal of gold and platinum from simulated as well as waste water solutions. Its potential viability as a biosorbent was demonstrated by the high recovery from synthetic solutions of greater than 99% for gold (2-10 mgIL), and greater than 89% for platinum (20 mgIL).
- Full Text:
- Date Issued: 2002
- Authors: Antunes, Ana Paula Martins
- Date: 2002
- Subjects: Azolla filiculoides Metal wastes -- Recycling Gold -- Recycling Platinum -- Recycling
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3894 , http://hdl.handle.net/10962/d1003726
- Description: Waste water from the mining industry is generally extremely complex and contains numerous species which influence the adsorption of the metals to any biomass. A variety of factors need to be addressed before treatment is considered viable. It is also beneficial to establish the binding characteristics of the metal of interest to maximise its interaction with the biomass to be utilised. Azalia filiculaides was investigated in the adsorption of gold(III), lead(II), iron(ID), copper(II) and platinum (IV). In batch studies, the optimum biomass and initial gold(III) concentrations were found to be 5 gIL and 8 mgIL respectively. The adsorption of gold(ID) is principally pH-dependent with optimal removal at pH 2. Lead(II), iron(III) and copper(II) did not compete with gold(III) adsorption under equimolar and simulated effluent conditions. Halides, with increasing affinity for gold (chloride < bromide < iodide), can affect gold uptake with the soft base, iodide, exhibiting the most inhibition (25%) and the hard base, chloride, O%. Mercaptoethanol (soft base) showed no interference in gold(III) adsorption while the presence of sulphate (hard base) and sulphite (borderline base) showed that concentrations in excess of 1 0 mM may adversely affect gold(ill) uptake, most likely due to competition for cationic sites on the biomass. Column studies, better suited to high volume treatment, indicated that a flow-rate of 5 mL/min and an initial gold(ill) concentration of 5 mgIL was optimal. Competitive effects between lead, iron, copper and gold again showed little or no interference. The halides, chloride, bromide and iodide, affect gold(ill) uptake similarly to the batch studies, while the bases mercaptoethanol and sulphate minimally affect gold(III) binding with sulphite severely hampering adsorption (70% inhibition). To optimise gold desorption, preliminary batch studies indicated that a ratio of 1:1 of adsorbentdesorbent was optimal, whilst gas purging of thiourea with oxygen, air and nitrogen decreased gold elution in proportion to decreased amounts of oxygen. A series of desorbents were utilised, in column studies, to optimise and determine the speciation of bound gold. The presence of an oxidant with thiourea enhanced desorption greater than 3 fold when compared with thiourea alone. Thiourea desorption studies, aided by the oxidant, suggest that gold is present in the + I and 0 oxidation states. Ultimately thiourea, perchloric acid and hydrochloric acid was found to be the most optimal elutant for gold (J 00% recovery). For selective metal recovery oflead and copper, pre-washing the plant material with water, utilising an acid (0.3 M nitric acid), pumping in an up-flow mode, and recycling the desorbent six times was found to be optimal elutant for gold (J 00% recovery). Cost analysis of utilising elutant versus incinerating the biomass for gold recovery indicated the latter as the most economical. Over a 5 cycle adsorption and desorption series, acid desorption before each adsorption cycle was found to result in greater than 92% desorption for lead and 96% for copper. Gold recovery was 97% with incineration. A preliminary study with gold effluent (Mine C) indicated that nickel and sulphate was removed in batch and column studies. Gold removal was found to be 100% and 4% in batch and column studies respectively. Adsorption of gold in the effluent study was accompanied by the release ofHt. Modifying the plant material with various reagents failed to identify the primary binding sites and the role of polysaccharides, proteins and lipids in gold(ill) uptake. The mode of gold binding is suggested as being initially ionic, this is very rapid, with the interaction of the anionic complex, [AuCI₄]". with the cationic biomass (PH 2). This eventually leads to the displacement of the chloride ligand(s) initiating covalent binding. Spectral studies of the chemical interaction between gold and the representative tannins indicated the protonated hydroxy groups to be responsible. All evidence suggests that the binding mechanisms of gold are not simple. Preliminary adsorption studies of platinum by Azalia filiculaides were conducted. Batch studies indicated that J gIL biomass concentration, initial platinum concentration of 20 mgIL and pH 2 are optimal, while the column studies indicated a flow-rate of! 0 rnL/min and initial platinum concentration of 20 mgIL as optimal. In the platinum effluent study, platinum showed a removal of 23 % and 2 J % for the batch and column studies respectively. Again adsorption was accompanied by //' release. Azalia filiculaides demonstrated its feasibility in the removal of gold and platinum from simulated as well as waste water solutions. Its potential viability as a biosorbent was demonstrated by the high recovery from synthetic solutions of greater than 99% for gold (2-10 mgIL), and greater than 89% for platinum (20 mgIL).
- Full Text:
- Date Issued: 2002
The biotransformation of phenolic pollutants using polyphenol oxidase
- Authors: Boshoff, Aileen
- Date: 2002
- Subjects: Polyphenol oxidase Sewage -- Purification
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3976 , http://hdl.handle.net/10962/d1004035
- Description: The potential of using mushroom polyphenol oxidase (EC 1.14.18.1) as a biocatalyst for the biotransformation of phenols to produce catechols in an aqueous medium was investigated. Polyphenol oxidase is characterised by two distinct reactions i.e., the ortho-hydroxylation of phenols to catechols (cresolase activity) and the subsequent oxidation of catechols to orthoquinones (catecholase activity). In order to facilitate the development of a process to produce catechols, the accumulation of catechol as a true intermediate product released in the reaction system needed to be investigated, as its release had been disputed due to the oxidation of catechols to o-quinones. Using LC-MS, catechol products were successfully identified as true intermediate products formed during biocatalytic reactions in water.
- Full Text:
- Date Issued: 2002
- Authors: Boshoff, Aileen
- Date: 2002
- Subjects: Polyphenol oxidase Sewage -- Purification
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3976 , http://hdl.handle.net/10962/d1004035
- Description: The potential of using mushroom polyphenol oxidase (EC 1.14.18.1) as a biocatalyst for the biotransformation of phenols to produce catechols in an aqueous medium was investigated. Polyphenol oxidase is characterised by two distinct reactions i.e., the ortho-hydroxylation of phenols to catechols (cresolase activity) and the subsequent oxidation of catechols to orthoquinones (catecholase activity). In order to facilitate the development of a process to produce catechols, the accumulation of catechol as a true intermediate product released in the reaction system needed to be investigated, as its release had been disputed due to the oxidation of catechols to o-quinones. Using LC-MS, catechol products were successfully identified as true intermediate products formed during biocatalytic reactions in water.
- Full Text:
- Date Issued: 2002
A historical study of John Graham Lake and South African/United States pentecostalism
- Authors: Burpeau, Kemp Pendleton
- Date: 2002
- Subjects: Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2587 , http://hdl.handle.net/10962/d1006484 , Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Description: American minister John Graham Lake (1870-1935) was a pivotal participant in an era of profound religious and political transition. Surprisingly, Lake's often provocative life had previously been largely neglected as a field of academic inquiry. In the U.S. Lake associated with key Holiness, Wesleyan and Apostolic Faith charismatics like John Alexander Dowie of the Zion City, Illinois Utopia, Charles Parham of the Topeka Revival and William Seymour of the Azusa Street Revival. Lake served as an important intermediary between Parham's often reactionary, white orientation that was unreceptive to an enthusiastic black liturgy and Seymour's expansive African-American egalitarianism expressed through exuberant spirit manifestations. Lake's South African ministry was shaped by his middle class white business background, Azusa Street message and American perspectives. He brought together the faith healing movement inspired by Dutch Reformed minister Andrew Murray, P. Ie Roux's black and white Zion charismatic adherents affiliated with Dowie and the new U.S. Pentecostalism of Parham and Seymour. Lake's African-American influenced Pentecostalism was compatible with indigenous African worship. His emphasis on the spiritual needs of the disempowered found a receptive audience in talented black evangelists Elias Letwaba and Edward Lion. Even though acquainted with Mohandas Gandhi, Lake did not undertake a South African social gospel-type civil protest against societal injustice. In fact, Lake's participation with Afrikaner politicians like Louis Botha in fashioning a segregationist land use law was most troubling. Lake was ambivalent about racial integration. His belief in an egalitarian status for all Christians, his Populist/Progressive ethics and his enthusiastic promotion of women's rights were complicated by his advocacy, or at least tolerance, of some disparate racial treatment in his Apostolic Faith Mission and South African society at large. Lake's paternalism and notion of Westem cultural superiority conflicted with his love of all persons. Lake's otherworldly prioritization of individual spiritualism over a socioeconomic agenda usually stymied activism. His uncharacteristic use of nonviolent protest to protect faith healing formed a remarkable contrast with his reluctance to actively campaign against unequal racial treatment in Africa and America. Historiographical perspectives on Lake range from the saintly pioneer charismatic missionary to the Elmer Gantry type charlatan acting only for personal benefit. Lake was a unique personality with his flamboyant rhetoric, strong convictions and feelings of personal worth. His distinctive Jesus as healing and suffering God theology evidenced both consistency with precedent as well as creative anticipation. Shortcomings resulting from his preference to address social concerns on an individual spiritual rather than societal level, his liberties with truth and his bad business judgments resulting in litigation. Nevertheless, Lake's life demonstrated that a gifted but imperfect instrument could accomplish a meaningful ministry. , Adobe Acrobat Pro 9.5.4 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
- Authors: Burpeau, Kemp Pendleton
- Date: 2002
- Subjects: Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2587 , http://hdl.handle.net/10962/d1006484 , Lake, John G , Pentecostalism -- South Africa , Pentecostalism -- United States , Pentecostals , Christianity and politics -- South Africa
- Description: American minister John Graham Lake (1870-1935) was a pivotal participant in an era of profound religious and political transition. Surprisingly, Lake's often provocative life had previously been largely neglected as a field of academic inquiry. In the U.S. Lake associated with key Holiness, Wesleyan and Apostolic Faith charismatics like John Alexander Dowie of the Zion City, Illinois Utopia, Charles Parham of the Topeka Revival and William Seymour of the Azusa Street Revival. Lake served as an important intermediary between Parham's often reactionary, white orientation that was unreceptive to an enthusiastic black liturgy and Seymour's expansive African-American egalitarianism expressed through exuberant spirit manifestations. Lake's South African ministry was shaped by his middle class white business background, Azusa Street message and American perspectives. He brought together the faith healing movement inspired by Dutch Reformed minister Andrew Murray, P. Ie Roux's black and white Zion charismatic adherents affiliated with Dowie and the new U.S. Pentecostalism of Parham and Seymour. Lake's African-American influenced Pentecostalism was compatible with indigenous African worship. His emphasis on the spiritual needs of the disempowered found a receptive audience in talented black evangelists Elias Letwaba and Edward Lion. Even though acquainted with Mohandas Gandhi, Lake did not undertake a South African social gospel-type civil protest against societal injustice. In fact, Lake's participation with Afrikaner politicians like Louis Botha in fashioning a segregationist land use law was most troubling. Lake was ambivalent about racial integration. His belief in an egalitarian status for all Christians, his Populist/Progressive ethics and his enthusiastic promotion of women's rights were complicated by his advocacy, or at least tolerance, of some disparate racial treatment in his Apostolic Faith Mission and South African society at large. Lake's paternalism and notion of Westem cultural superiority conflicted with his love of all persons. Lake's otherworldly prioritization of individual spiritualism over a socioeconomic agenda usually stymied activism. His uncharacteristic use of nonviolent protest to protect faith healing formed a remarkable contrast with his reluctance to actively campaign against unequal racial treatment in Africa and America. Historiographical perspectives on Lake range from the saintly pioneer charismatic missionary to the Elmer Gantry type charlatan acting only for personal benefit. Lake was a unique personality with his flamboyant rhetoric, strong convictions and feelings of personal worth. His distinctive Jesus as healing and suffering God theology evidenced both consistency with precedent as well as creative anticipation. Shortcomings resulting from his preference to address social concerns on an individual spiritual rather than societal level, his liberties with truth and his bad business judgments resulting in litigation. Nevertheless, Lake's life demonstrated that a gifted but imperfect instrument could accomplish a meaningful ministry. , Adobe Acrobat Pro 9.5.4 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
The growth and reproduction of the freshwater limpet Burnupia stenochorias (Pulmonata, Ancylidae), and an evaluation of its use as an ecotoxicology indicator in whole effluent testing
- Davies-Coleman, H D (Heather D)
- Authors: Davies-Coleman, H D (Heather D)
- Date: 2002
- Subjects: Ancylidae Effluent quality Toxicity testing
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5703 , http://hdl.handle.net/10962/d1005389
- Description: For the protection of the ecological Reserve in South Africa, the proposed introduction of compulsory toxicity testing in the licensing of effluent discharges necessitates the development of whole effluent toxicity testing. The elucidation of the effects of effluent on the local indigenous populations of organisms is essential before hazard and risk assessment can be undertaken. The limpet Burnupia stenochorias, prevalent in the Eastern Cape of South Africa, was chosen to represent the freshwater molluscs as a potential toxicity indicator. Using potassium dichromate (as a reference toxicant) and a textile whole effluent, the suitability of B. stenochorias was assessed under both acute and chronic toxicity conditions in the laboratory. In support of the toxicity studies, aspects of the biology of B. stenochorias were investigated under both natural and laboratory conditions. Using Principal Component and Discriminant Function Analyses, the relative shell morphometrics of three feral populations of B. stenochorias were found to vary. Length was shown to adequately represent growth of the shell, although the inclusion of width measurements is more statistically preferable. Two of the feral populations, one in impacted water, were studied weekly for 52 weeks to assess natural population dynamics. Based on the Von Bertalanffy Growth Equation, estimates of growth and longevity were made for this species, with growth highly seasonal. Age is not easily discerned from shell size. Egg laying occurred all year round, with early summer (peak egg lay), mid summer (a second, smaller peak in egg lay), and winter (limited presence of eggs) phases. In toxicity testing, consideration is given to the choice of the test organism based on age and sexual development. Consequently, the sexual development of B. stenochorias relative to shell length was determined with the aid of histological examinations of transverse sections of limpets, of all sizes, collected over one year. Limpets less than 3mm shell length were found to be immature in the development of the oocytes and spermatozoa, and were later chosen for acute toxicity tests. A laboratory diet was developed, for both culturing and maintaining of the limpets during toxicity tests; however, the diet requires optimisation. Under laboratory conditions, growth was linear, and individual fecundity highly variable. Successful methods for the collection of limpets from naturally occurring populations, and their acclimation to the laboratory were developed. Three B. stenochorias populations, representing different hydrological and water quality conditions, were compared to a laboratory population (maintained for three years) in their responses to the textile whole effluent and potassium dichromate. Under acute conditions, variability of mortality between limpet populations and between seasons was consistent with acceptable international standards. However, seasonal differences between feral limpets were apparent, with early summer limpets significantly more susceptible to both potassium dichromate and textile effluent than winter limpets. Although mortality occurred within the effluent at all concentrations, no 96 hour LC₅₀ values were obtained. The chronic toxicity effects of the textile whole effluent were assessed over the entire life cycle of B. stenochorias, based on survival, growth and reproductive effects. Lower concentrations of effluent (# 10%) gave greater variability of responses and toxicity than higher concentrations, with a 43 day LC₅₀ of 3.9% effluent. The No Observed Effect Concentrations for survival (over 43 days) were calculated in consecutive years as 0.1% and 1% effluent. Survival is considered a useful tool for determining toxicity endpoints using B. stenochorias. Limpet growth remained linear in effluent, with an apparent stimulation of growth at the 3-10% effluent concentration, confusing the toxicity and variability assessments. The possible addition of nutrients from the effluent points to either a potential inadequacy of the food quality provided in the chronic assessment, or the presence in the effluent of growth stimulants. Growth was also found to be too variable to allow adequate statistical conclusions about the toxicity of the effluent, although it is suggested that growth may be useful in the assessment of single compounds. Despite large individual variability in fecundity, statistical differences were discernible between effluent concentrations. The application of fecundity of B. stenochorias in hazard assessment therefore warrants further investigation. It was concluded that an assessment of textile whole effluent toxicity to B. stenochorias over an entire life cycle, and an F1 generation, is unnecessary. The development of the bucket/plastic bag method for both acute and chronic toxicity assessment of B. stenochorias was useful. In the final assessment of the usefulness of B. stenochorias as a toxicity indicator, toxicity endpoints were compared with those of the standard laboratory organism Daphnia pulex. Both in acute and chronic toxicity, B. stenochorias was found to be more sensitive. B. stenochorias is therefore considered valuable as a South African freshwater molluscan ecotoxicological indicator, with a place in hazard assessment, although further development and research is necessary before the limpet can be effectively used.
- Full Text:
- Date Issued: 2002
- Authors: Davies-Coleman, H D (Heather D)
- Date: 2002
- Subjects: Ancylidae Effluent quality Toxicity testing
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5703 , http://hdl.handle.net/10962/d1005389
- Description: For the protection of the ecological Reserve in South Africa, the proposed introduction of compulsory toxicity testing in the licensing of effluent discharges necessitates the development of whole effluent toxicity testing. The elucidation of the effects of effluent on the local indigenous populations of organisms is essential before hazard and risk assessment can be undertaken. The limpet Burnupia stenochorias, prevalent in the Eastern Cape of South Africa, was chosen to represent the freshwater molluscs as a potential toxicity indicator. Using potassium dichromate (as a reference toxicant) and a textile whole effluent, the suitability of B. stenochorias was assessed under both acute and chronic toxicity conditions in the laboratory. In support of the toxicity studies, aspects of the biology of B. stenochorias were investigated under both natural and laboratory conditions. Using Principal Component and Discriminant Function Analyses, the relative shell morphometrics of three feral populations of B. stenochorias were found to vary. Length was shown to adequately represent growth of the shell, although the inclusion of width measurements is more statistically preferable. Two of the feral populations, one in impacted water, were studied weekly for 52 weeks to assess natural population dynamics. Based on the Von Bertalanffy Growth Equation, estimates of growth and longevity were made for this species, with growth highly seasonal. Age is not easily discerned from shell size. Egg laying occurred all year round, with early summer (peak egg lay), mid summer (a second, smaller peak in egg lay), and winter (limited presence of eggs) phases. In toxicity testing, consideration is given to the choice of the test organism based on age and sexual development. Consequently, the sexual development of B. stenochorias relative to shell length was determined with the aid of histological examinations of transverse sections of limpets, of all sizes, collected over one year. Limpets less than 3mm shell length were found to be immature in the development of the oocytes and spermatozoa, and were later chosen for acute toxicity tests. A laboratory diet was developed, for both culturing and maintaining of the limpets during toxicity tests; however, the diet requires optimisation. Under laboratory conditions, growth was linear, and individual fecundity highly variable. Successful methods for the collection of limpets from naturally occurring populations, and their acclimation to the laboratory were developed. Three B. stenochorias populations, representing different hydrological and water quality conditions, were compared to a laboratory population (maintained for three years) in their responses to the textile whole effluent and potassium dichromate. Under acute conditions, variability of mortality between limpet populations and between seasons was consistent with acceptable international standards. However, seasonal differences between feral limpets were apparent, with early summer limpets significantly more susceptible to both potassium dichromate and textile effluent than winter limpets. Although mortality occurred within the effluent at all concentrations, no 96 hour LC₅₀ values were obtained. The chronic toxicity effects of the textile whole effluent were assessed over the entire life cycle of B. stenochorias, based on survival, growth and reproductive effects. Lower concentrations of effluent (# 10%) gave greater variability of responses and toxicity than higher concentrations, with a 43 day LC₅₀ of 3.9% effluent. The No Observed Effect Concentrations for survival (over 43 days) were calculated in consecutive years as 0.1% and 1% effluent. Survival is considered a useful tool for determining toxicity endpoints using B. stenochorias. Limpet growth remained linear in effluent, with an apparent stimulation of growth at the 3-10% effluent concentration, confusing the toxicity and variability assessments. The possible addition of nutrients from the effluent points to either a potential inadequacy of the food quality provided in the chronic assessment, or the presence in the effluent of growth stimulants. Growth was also found to be too variable to allow adequate statistical conclusions about the toxicity of the effluent, although it is suggested that growth may be useful in the assessment of single compounds. Despite large individual variability in fecundity, statistical differences were discernible between effluent concentrations. The application of fecundity of B. stenochorias in hazard assessment therefore warrants further investigation. It was concluded that an assessment of textile whole effluent toxicity to B. stenochorias over an entire life cycle, and an F1 generation, is unnecessary. The development of the bucket/plastic bag method for both acute and chronic toxicity assessment of B. stenochorias was useful. In the final assessment of the usefulness of B. stenochorias as a toxicity indicator, toxicity endpoints were compared with those of the standard laboratory organism Daphnia pulex. Both in acute and chronic toxicity, B. stenochorias was found to be more sensitive. B. stenochorias is therefore considered valuable as a South African freshwater molluscan ecotoxicological indicator, with a place in hazard assessment, although further development and research is necessary before the limpet can be effectively used.
- Full Text:
- Date Issued: 2002
Elucidation and manipulation of the Hydantoin-Hydrolysing Enzyme System of Agrobacterium tumefaciens RU-OR for the Biocatalytic production of D-amino acids
- Authors: Hartley, Carol Janet
- Date: 2002
- Subjects: Amino acids Agrobacterium tumefaciens
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3916 , http://hdl.handle.net/10962/d1003975
- Description: There is widespread interest in the biocatalytic production of enantiomerically pure D-amino acids for use in the synthesis of antibiotics, insecticides, herbicides, drug carriers and many other pharmaceuticals. Hydantoin-hydrolysing enzyme systems can be successfully utilised to stereoselectively convert racemic hydantoins into enantiomerically pure amino acid products. In fact, the use of microbial D-hydantoinase and D-stereoselective N-carbamoyl amino acid amidohydrolase activity to produce D-p-hydroxyphenylglycine from D,L-5-phydroxyphenylhydantoin has been described as one of the most successful biotechnological applications of enzyme technology developed to date. A need to utilise the novel biodiversity of South African microorganisms for the development of an indigenous process to produce enantiomerically pure amino acids was identified in 1995. Subsequently, the Rhodes Hydantoinase Group was established and several local hydantoin-hydrolysing microorganisms were isolated. The research in this study describes the isolation and selection of Agrobacterium tumefaciens RU-OR, which produced D-stereoselective hydantoinhydrolysing activity. Characterisation of the hydantoin-hydrolysing enzyme system of RU-OR revealed novel biocatalytic properties, and potential for the application of this strain for the biocatalytic production of D-amino acids. A fundamental understanding of the regulation of hydantoin-hydrolysing enzyme activity in A. tumefaciens RU-OR was established, and utilised to produce mutant strains with altered regulation of hydantoin-hydrolysing activity. These strains were used to further elucidate the mechanisms regulating the production of hydantoins-hydrolysing activity in A. tumefaciens RU-OR cells. Overproduction of hydantoinase and N-carbamoyl-D-amino acid amidohydrolase activity in selected mutant strains resulted in efficient conversion of D,L-5-p-hydroxyphenylhydantoin to D-p-hydroxyphenylglycine. Thus the establishment of a primary understanding of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR could be used to manipulate the hydantoin-hydrolysing activity in RU-OR cells to produce an improved biocatalyst. The isolation of A. tumfecaiens RU-OR genes encoding for hydantoin-hydrolysing activity revealed two separate N-carbamoyl-D-amino acid amidohydrolaseencoding genes (ncaR1 and ncaR2) in this bacterium with distinct chromosomal locations, nucleotide coding sequence and predicted primary amino acid sequence. The novel biocatalytic properties of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR and mutant derivatives present fascinating opportunities for further elucidation of the natural function, regulation and biocatalytic potential of hydantoin-hydrolysing enzymes.
- Full Text:
- Date Issued: 2002
- Authors: Hartley, Carol Janet
- Date: 2002
- Subjects: Amino acids Agrobacterium tumefaciens
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3916 , http://hdl.handle.net/10962/d1003975
- Description: There is widespread interest in the biocatalytic production of enantiomerically pure D-amino acids for use in the synthesis of antibiotics, insecticides, herbicides, drug carriers and many other pharmaceuticals. Hydantoin-hydrolysing enzyme systems can be successfully utilised to stereoselectively convert racemic hydantoins into enantiomerically pure amino acid products. In fact, the use of microbial D-hydantoinase and D-stereoselective N-carbamoyl amino acid amidohydrolase activity to produce D-p-hydroxyphenylglycine from D,L-5-phydroxyphenylhydantoin has been described as one of the most successful biotechnological applications of enzyme technology developed to date. A need to utilise the novel biodiversity of South African microorganisms for the development of an indigenous process to produce enantiomerically pure amino acids was identified in 1995. Subsequently, the Rhodes Hydantoinase Group was established and several local hydantoin-hydrolysing microorganisms were isolated. The research in this study describes the isolation and selection of Agrobacterium tumefaciens RU-OR, which produced D-stereoselective hydantoinhydrolysing activity. Characterisation of the hydantoin-hydrolysing enzyme system of RU-OR revealed novel biocatalytic properties, and potential for the application of this strain for the biocatalytic production of D-amino acids. A fundamental understanding of the regulation of hydantoin-hydrolysing enzyme activity in A. tumefaciens RU-OR was established, and utilised to produce mutant strains with altered regulation of hydantoin-hydrolysing activity. These strains were used to further elucidate the mechanisms regulating the production of hydantoins-hydrolysing activity in A. tumefaciens RU-OR cells. Overproduction of hydantoinase and N-carbamoyl-D-amino acid amidohydrolase activity in selected mutant strains resulted in efficient conversion of D,L-5-p-hydroxyphenylhydantoin to D-p-hydroxyphenylglycine. Thus the establishment of a primary understanding of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR could be used to manipulate the hydantoin-hydrolysing activity in RU-OR cells to produce an improved biocatalyst. The isolation of A. tumfecaiens RU-OR genes encoding for hydantoin-hydrolysing activity revealed two separate N-carbamoyl-D-amino acid amidohydrolaseencoding genes (ncaR1 and ncaR2) in this bacterium with distinct chromosomal locations, nucleotide coding sequence and predicted primary amino acid sequence. The novel biocatalytic properties of the hydantoin-hydrolysing enzyme system in A. tumefaciens RU-OR and mutant derivatives present fascinating opportunities for further elucidation of the natural function, regulation and biocatalytic potential of hydantoin-hydrolysing enzymes.
- Full Text:
- Date Issued: 2002
The medicinal chemistry of the isomers of the cyclic dipeptide: cyclo(Trp-Pro)
- Authors: Jamie, Hajierah
- Date: 2002
- Subjects: Pharmaceutical chemistry , Cyclic compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11023 , http://hdl.handle.net/10948/281 , Pharmaceutical chemistry , Cyclic compounds
- Description: The isomers of cyclo(Trp-Pro) (cyclo(L-Trp-L-Pro), cyclo(L-Trp-D-Pro), cyclo(D-Trp-LPro) and cyclo(D-Trp-D-Pro)) have been successfully synthesized and screened for biological activity. High percentage yields were obtained by using the three phase synthesis system, which involves the synthesis of the intermediate protected linear dipeptides, followed by the removal of the protecting Boc groups. This step is followed by cyclization and crystallization of the isomers. The diketopiperazines rings of cyclo(L-Trp-L-Pro) and cyclo(D-Trp-D-Pro) contain cisamide bonds, while cyclo(L-Trp-D-Pro) and cyclo(D-Trp-L-Pro) contain trans-amide bonds. These bonds govern the conformation of the diketopiperazines ring. The isomers have shown different degrees of biological activity, possibly as a result of the orientation of the side chain of tryptophan and this difference in conformation, leading to varying interactions between isomer and a range of receptors. Under experimental conditions, 10-3 M cyclo(L-Trp-D-Pro) and cyclo(D-Trp-L-Pro) showed effective anticancer activity against the cervical cancer cell line, HeLa, resulting in a <50% reduction in cell viability. Cytotoxicity screening with cyclo(D-Trp-L-Pro) indicated that it was hepatocyte-specific in its toxicity, whilst the other isomers were cytotoxic against the other cell types tested. At 1mg/ml, cyclo(L-Trp-L-Pro) proved to be an effective antimicrobial agent against Gram positive bacteria, while cyclo(L-Trp-DPro) effectively inhibited the growth of the Gram negative bacteria, Esherichia coli. Cyclo(D-Trp-L-Pro) proved to be effective against Streptococcus, while cyclo(D-Trp-DPro) effectively reduced viability of the yeast, Candida albicans. Cyclo(D-Trp-L-Pro) was the only isomer to show Ca2+-channel antagonism, whilst the other isomers resulted in opening of the Ca2+-channel. No effects were observed on K+-channel activity for all the isomers tested. The isomers also proved to be valuable antiarrhythmic agents by effectively reducing the time spent in ventricular tachycardia and arrhythmia, as well as decreasing the time for the heart rate to return to a normal sinus rhythm. Furthermore, cyclo(L-Trp-D-Pro) showed positive chronotropic activity, while cyclo(D-Trp-L-Pro) ii showed negative chronotropic activity. In addition, cyclo(L-Trp-D-Pro) and cyclo(D-Trp- L-Pro) also increased the coronary flow rate. 0.125 1 mM Cyclo(L-Trp-D-Pro) decreased aggregation in washed platelets induced by thrombin. All isomers increased adhesion to an artificial surface when the platelets were stimulated by ADP, yet caused reduced adhesion when the platelets were stimulated by thrombin. These results prove the potential of these compounds as novel agents in a range of biological fields, indicating that a combination of L- and D- amino acids may prove more effective than an agent consisting solely of L-amino acids.
- Full Text:
- Date Issued: 2002
- Authors: Jamie, Hajierah
- Date: 2002
- Subjects: Pharmaceutical chemistry , Cyclic compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:11023 , http://hdl.handle.net/10948/281 , Pharmaceutical chemistry , Cyclic compounds
- Description: The isomers of cyclo(Trp-Pro) (cyclo(L-Trp-L-Pro), cyclo(L-Trp-D-Pro), cyclo(D-Trp-LPro) and cyclo(D-Trp-D-Pro)) have been successfully synthesized and screened for biological activity. High percentage yields were obtained by using the three phase synthesis system, which involves the synthesis of the intermediate protected linear dipeptides, followed by the removal of the protecting Boc groups. This step is followed by cyclization and crystallization of the isomers. The diketopiperazines rings of cyclo(L-Trp-L-Pro) and cyclo(D-Trp-D-Pro) contain cisamide bonds, while cyclo(L-Trp-D-Pro) and cyclo(D-Trp-L-Pro) contain trans-amide bonds. These bonds govern the conformation of the diketopiperazines ring. The isomers have shown different degrees of biological activity, possibly as a result of the orientation of the side chain of tryptophan and this difference in conformation, leading to varying interactions between isomer and a range of receptors. Under experimental conditions, 10-3 M cyclo(L-Trp-D-Pro) and cyclo(D-Trp-L-Pro) showed effective anticancer activity against the cervical cancer cell line, HeLa, resulting in a <50% reduction in cell viability. Cytotoxicity screening with cyclo(D-Trp-L-Pro) indicated that it was hepatocyte-specific in its toxicity, whilst the other isomers were cytotoxic against the other cell types tested. At 1mg/ml, cyclo(L-Trp-L-Pro) proved to be an effective antimicrobial agent against Gram positive bacteria, while cyclo(L-Trp-DPro) effectively inhibited the growth of the Gram negative bacteria, Esherichia coli. Cyclo(D-Trp-L-Pro) proved to be effective against Streptococcus, while cyclo(D-Trp-DPro) effectively reduced viability of the yeast, Candida albicans. Cyclo(D-Trp-L-Pro) was the only isomer to show Ca2+-channel antagonism, whilst the other isomers resulted in opening of the Ca2+-channel. No effects were observed on K+-channel activity for all the isomers tested. The isomers also proved to be valuable antiarrhythmic agents by effectively reducing the time spent in ventricular tachycardia and arrhythmia, as well as decreasing the time for the heart rate to return to a normal sinus rhythm. Furthermore, cyclo(L-Trp-D-Pro) showed positive chronotropic activity, while cyclo(D-Trp-L-Pro) ii showed negative chronotropic activity. In addition, cyclo(L-Trp-D-Pro) and cyclo(D-Trp- L-Pro) also increased the coronary flow rate. 0.125 1 mM Cyclo(L-Trp-D-Pro) decreased aggregation in washed platelets induced by thrombin. All isomers increased adhesion to an artificial surface when the platelets were stimulated by ADP, yet caused reduced adhesion when the platelets were stimulated by thrombin. These results prove the potential of these compounds as novel agents in a range of biological fields, indicating that a combination of L- and D- amino acids may prove more effective than an agent consisting solely of L-amino acids.
- Full Text:
- Date Issued: 2002
The life history of selected coastal foredune species of South Africa
- Authors: Knevel, Irma Cornelia
- Date: 2002
- Subjects: Sand dune plants -- South Africa Sand dune ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4207 , http://hdl.handle.net/10962/d1003776
- Description: South African dune fields are severely threatened by human expansion and in the long run the stabilisation of many dunes will be necessary. The alien grass Ammophila arenaria is the most important drift sand stabiliser at present in South Africa. Although not invasive, the current impact of A. arenaria on the dune systems of South Africa is considerable, and thus the stabilising benefit of the grass seemed to may be outweighed by its negative consequences. It is therefore preferable to use indigenous sand stabilising species. In order to define guidelines for the application of indigenous plants for stabilisation, their autecology should be studied first to enhance the chance of successful stabilisation results. The main aim of the present thesis was to gather information on the life history processes of selected indigenous, sand stabilising foredune species. To investigate the growth of foredune pioneer species, the common pioneer Scaevola plumieri was followed over a three-year period to determine the growth season and leaf phenology. Soil-borne pathogens are known to influence the growth and vegetation dynamics of foredune species. To examine this effect on the South African foredunes the rhizosphere soil and the roots of several species were studied. To test the effect of the nematode fauna on succeeding plant species a transplantation experiment was carried out. The seed stage is the only life-cycle stage that can survive unfavourable conditions. Therefore, the seed ecology of several foredune species was studied extensively to determine the reproductive season, the seed production, the fate of seeds after shedding (germination, seawater dispersal), germination requirements and seed bank strategy. Seeds of the species Arctotheca populifolia, Ipomoea pes-caprae, Myrica cordifolia, and Scaevola plumieri were subjected to germination trials, field observations on seedling survival, and scarification and stratification experiments. This was done to obtain information about the germination requirements and to determine the reproductive season and growth season. The seed bank strategy of the foredune species, as well as the seed bank density, was determined by extensive sampling along the Cape coast. The species S. plumieri thrived under sand accretion situations, which makes it a good candidate for stabilisation purposes. The growth of S. plumieri was seasonal, with the highest leaf production during spring and summer. The stem position on the foredune had a strong effect on the overall performance of S. plumieri , with the stems situated on the landward face of the foredune showing higher leaf and seed production. Theiii nematode survey of soil and roots of several foredune species showed that all plant species featured a specific nematode fauna in the rhizosphere soil and the roots. The specific nematode fauna affected the growth of foreign plant species in the transplantation experiment, resulting in a lower root and/or shoot biomass production. Most of the foredune species produce seeds from spring to late summer. For S. plumieri the position of the stem on the dunes, as well as the predation of unripe seeds affected the number of seeds produced. The highest production was found for the landward faced stems. The S. plumieri seeds were able to float on seawater for at least three months without losing viability, as was observed for seeds of I. pes-caprae. The seeds of M. cordifolia, however, sank after a few days, but their viability was not affected. The rhizome fragments of A. arenaria and S. virginicus floated for 120 days, whereas the fragments of E. villosa sunk after one day. The viability of S. virginicus fragments was affected by the duration in seawater by an increase in sprouting time. The seeds of all species tested germinated readily under controlled conditions, except S. plumieri seeds which required a long lag-phase before germination. In the field the seeds of A. populifolia, I. pes-caprae and S. plumieri germinated, producing many seedlings. Only the seedlings of A. populifolia and S. plumieri survived. Of the species found in the foredunes 57% was represented in the soil seed bank. For most species, the seeds that were found in the seed bank showed viability of at least 40%. Many of the seeds found were older than one year, suggesting a short-term persistent seed bank. The present study is a start in filling the gap in information on dune pioneer and foredune species. The conclusion was that in general all species in the present study were easy to grow under controlled conditions, and thus could be used for stabilisation purposes. When the more rapidly growing pioneer species are planted in combination with succeeding foredune species, a functional and aesthetic ecosystem could be created.
- Full Text:
- Date Issued: 2002
- Authors: Knevel, Irma Cornelia
- Date: 2002
- Subjects: Sand dune plants -- South Africa Sand dune ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4207 , http://hdl.handle.net/10962/d1003776
- Description: South African dune fields are severely threatened by human expansion and in the long run the stabilisation of many dunes will be necessary. The alien grass Ammophila arenaria is the most important drift sand stabiliser at present in South Africa. Although not invasive, the current impact of A. arenaria on the dune systems of South Africa is considerable, and thus the stabilising benefit of the grass seemed to may be outweighed by its negative consequences. It is therefore preferable to use indigenous sand stabilising species. In order to define guidelines for the application of indigenous plants for stabilisation, their autecology should be studied first to enhance the chance of successful stabilisation results. The main aim of the present thesis was to gather information on the life history processes of selected indigenous, sand stabilising foredune species. To investigate the growth of foredune pioneer species, the common pioneer Scaevola plumieri was followed over a three-year period to determine the growth season and leaf phenology. Soil-borne pathogens are known to influence the growth and vegetation dynamics of foredune species. To examine this effect on the South African foredunes the rhizosphere soil and the roots of several species were studied. To test the effect of the nematode fauna on succeeding plant species a transplantation experiment was carried out. The seed stage is the only life-cycle stage that can survive unfavourable conditions. Therefore, the seed ecology of several foredune species was studied extensively to determine the reproductive season, the seed production, the fate of seeds after shedding (germination, seawater dispersal), germination requirements and seed bank strategy. Seeds of the species Arctotheca populifolia, Ipomoea pes-caprae, Myrica cordifolia, and Scaevola plumieri were subjected to germination trials, field observations on seedling survival, and scarification and stratification experiments. This was done to obtain information about the germination requirements and to determine the reproductive season and growth season. The seed bank strategy of the foredune species, as well as the seed bank density, was determined by extensive sampling along the Cape coast. The species S. plumieri thrived under sand accretion situations, which makes it a good candidate for stabilisation purposes. The growth of S. plumieri was seasonal, with the highest leaf production during spring and summer. The stem position on the foredune had a strong effect on the overall performance of S. plumieri , with the stems situated on the landward face of the foredune showing higher leaf and seed production. Theiii nematode survey of soil and roots of several foredune species showed that all plant species featured a specific nematode fauna in the rhizosphere soil and the roots. The specific nematode fauna affected the growth of foreign plant species in the transplantation experiment, resulting in a lower root and/or shoot biomass production. Most of the foredune species produce seeds from spring to late summer. For S. plumieri the position of the stem on the dunes, as well as the predation of unripe seeds affected the number of seeds produced. The highest production was found for the landward faced stems. The S. plumieri seeds were able to float on seawater for at least three months without losing viability, as was observed for seeds of I. pes-caprae. The seeds of M. cordifolia, however, sank after a few days, but their viability was not affected. The rhizome fragments of A. arenaria and S. virginicus floated for 120 days, whereas the fragments of E. villosa sunk after one day. The viability of S. virginicus fragments was affected by the duration in seawater by an increase in sprouting time. The seeds of all species tested germinated readily under controlled conditions, except S. plumieri seeds which required a long lag-phase before germination. In the field the seeds of A. populifolia, I. pes-caprae and S. plumieri germinated, producing many seedlings. Only the seedlings of A. populifolia and S. plumieri survived. Of the species found in the foredunes 57% was represented in the soil seed bank. For most species, the seeds that were found in the seed bank showed viability of at least 40%. Many of the seeds found were older than one year, suggesting a short-term persistent seed bank. The present study is a start in filling the gap in information on dune pioneer and foredune species. The conclusion was that in general all species in the present study were easy to grow under controlled conditions, and thus could be used for stabilisation purposes. When the more rapidly growing pioneer species are planted in combination with succeeding foredune species, a functional and aesthetic ecosystem could be created.
- Full Text:
- Date Issued: 2002
Biosulphidogenic hydrolysis of lignin and lignin model compounds
- Authors: Madikane, Mzekelo
- Date: 2002
- Subjects: Lignin Lignin -- Biodegradation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3917 , http://hdl.handle.net/10962/d1003976
- Description: Lignin degradation under biosulphidogenic conditions has not been extensively reported in the literature. Although aerobic degradation of lignin is well documented, anaerobic biodegradation has focused mainly on methanogenic systems with biosulphidogenic systems receiving less attention. Sulphate reducing bacteria are known to generate moderately high levels of both sulphide and alkalinity at room temperatures, and these conditions draw some comparison with the Kraft pulping process. In the Kraft pulping process, lignin is degraded chemically at ±170°C under high sulphide and alkaline conditions and may provide a model for understanding biosulphidogenic lignin degrading activity. The aim of this study was to investigate the biosulphidogenic hydrolysis of lignin within the context of the chemical and biological conditions generated by a mixed sulphate reducing bacteria consortia. Bioreactor studies with a mixed sulphate reducing consortia and pine wood powder (both untreated and depectinated) resulted in the generation of comparable levels of sulphide and alkalinity used in the chemical hydrolysis studies. Aromatic compound yields were between 20 to 50% of the chemical hydrolysis studies. This fluctuation may have been due to the utilization of these aromatic compounds as electron donors by the sulphate reducing consortia as evidenced by the high rate of sulphate reduction in both the untreated and depectinated wood bioreactors. Biodegradation of lignin model compounds was investigated in order to elucidate lignin degradation mechanisms. Both mono-aromatic and dimeric lignin model compounds were used as electron donors and carbon sources for the mixed sulphate reducing consortia. Biodegradation and mass spectrometer analysis of mono-aromatic compounds, ferulic acid and ferulic acid ethyl ester resulted in the production of intermediates such as catechol, cyclohexane carboxylic acid and adipic acid. These intermediates were also observed in the degradation of dimeric ferulic acid. Biodegradation of salicin resulted in the production of salicyl alcohol, ortho-cresol and acetate. Biodegradation of benzylic ether resulted in the production of vanillin and acetate as end products. The results of these studies provide evidence for a biosulphidogenic hydrolysis of lignin, and also the utilisation of lignin-derived aromatic compounds as electron donor sources, by a mixed sulphate reducing consortia.
- Full Text:
- Date Issued: 2002
- Authors: Madikane, Mzekelo
- Date: 2002
- Subjects: Lignin Lignin -- Biodegradation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:3917 , http://hdl.handle.net/10962/d1003976
- Description: Lignin degradation under biosulphidogenic conditions has not been extensively reported in the literature. Although aerobic degradation of lignin is well documented, anaerobic biodegradation has focused mainly on methanogenic systems with biosulphidogenic systems receiving less attention. Sulphate reducing bacteria are known to generate moderately high levels of both sulphide and alkalinity at room temperatures, and these conditions draw some comparison with the Kraft pulping process. In the Kraft pulping process, lignin is degraded chemically at ±170°C under high sulphide and alkaline conditions and may provide a model for understanding biosulphidogenic lignin degrading activity. The aim of this study was to investigate the biosulphidogenic hydrolysis of lignin within the context of the chemical and biological conditions generated by a mixed sulphate reducing bacteria consortia. Bioreactor studies with a mixed sulphate reducing consortia and pine wood powder (both untreated and depectinated) resulted in the generation of comparable levels of sulphide and alkalinity used in the chemical hydrolysis studies. Aromatic compound yields were between 20 to 50% of the chemical hydrolysis studies. This fluctuation may have been due to the utilization of these aromatic compounds as electron donors by the sulphate reducing consortia as evidenced by the high rate of sulphate reduction in both the untreated and depectinated wood bioreactors. Biodegradation of lignin model compounds was investigated in order to elucidate lignin degradation mechanisms. Both mono-aromatic and dimeric lignin model compounds were used as electron donors and carbon sources for the mixed sulphate reducing consortia. Biodegradation and mass spectrometer analysis of mono-aromatic compounds, ferulic acid and ferulic acid ethyl ester resulted in the production of intermediates such as catechol, cyclohexane carboxylic acid and adipic acid. These intermediates were also observed in the degradation of dimeric ferulic acid. Biodegradation of salicin resulted in the production of salicyl alcohol, ortho-cresol and acetate. Biodegradation of benzylic ether resulted in the production of vanillin and acetate as end products. The results of these studies provide evidence for a biosulphidogenic hydrolysis of lignin, and also the utilisation of lignin-derived aromatic compounds as electron donor sources, by a mixed sulphate reducing consortia.
- Full Text:
- Date Issued: 2002
A comparative study of atmospheric dynamics in the mesosphere and lower thermosphere (MLT) near Grahamstown (South Africa) and Adelaide (Australia)
- Authors: Malinga, Sandile Bethuel
- Date: 2002
- Subjects: Atmospheric physics Atmospheric physics -- South Africa -- Eastern Cape Atmospheric physics -- Australia Dynamic meteorology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5506 , http://hdl.handle.net/10962/d1007307
- Description: The observations made near Grahamstown (33 .3°S, 26.5°E), South Africa and Adelaide (34.5°S, 138.5°E), Australia over the years 1987 to 1994 are used to study the dynamics of the mesosphere and lower thermosphere (ML T) region with a focus on ∼ 90 km altitude. In particular this thesis deals with on the atmospheric mean flow and the solar diurnal and semi diurnal oscillations with a view to (i) deducing their patterns at the two sites, (ii) comparing the dynamic structures observed at the two sites with special emphases on longitudinal variations, and (iii) putting these observations in a global context by comparing with other ground-based observations, satellite observations and numerical simulations. The main findings are summarised below. The mean flow and the tides at Grahamstown and Adelaide are characteristically variable at planetary time scales. Wavelet spectral and multiresolution analyses reveal that the dominant planetary oscillation is the quasi-16-day oscillation. However, no apparent correlation in the 16-day waves of the mean flow, the diurnal tide and the semidiurnal tide was found. The short-term fluctuations were also investigated using complex demodulation and bispectral techniques and it was found that some of the observed variations in tides could be due to non-linear wave-wave interactions. The long-term trends of the mean flow and tides show patterns that are in broad agreement with theory, results from elsewhere (ground-based and satellite) and the results of the Global-Scale Wave Model and various models by Portnyagin and others. In general the mean flow, the amplitudes and phases of both tides were found to exhibit seasonal and interannual variations which are thought to be related to various factors including (i) changes in the atmospheric mean environment, (ii) thermotidal forcing (iii) gravity wave effects, (iv) planetary scale influence, (v) long-term (e.g. quasi-biennial oscillation) modulation, and (vi) solar activity. There are significant longitudinal differences in the dynamic structure between Grahamstown and Adelaide. More especially, Grahamstown tends to have stronger mean flow and tidal activity than Adelaide. For tides, these differences are thought to be partly due to nonmigrating tidal modes but, in general, migrating modes were found to be dominant.
- Full Text:
- Date Issued: 2002
- Authors: Malinga, Sandile Bethuel
- Date: 2002
- Subjects: Atmospheric physics Atmospheric physics -- South Africa -- Eastern Cape Atmospheric physics -- Australia Dynamic meteorology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5506 , http://hdl.handle.net/10962/d1007307
- Description: The observations made near Grahamstown (33 .3°S, 26.5°E), South Africa and Adelaide (34.5°S, 138.5°E), Australia over the years 1987 to 1994 are used to study the dynamics of the mesosphere and lower thermosphere (ML T) region with a focus on ∼ 90 km altitude. In particular this thesis deals with on the atmospheric mean flow and the solar diurnal and semi diurnal oscillations with a view to (i) deducing their patterns at the two sites, (ii) comparing the dynamic structures observed at the two sites with special emphases on longitudinal variations, and (iii) putting these observations in a global context by comparing with other ground-based observations, satellite observations and numerical simulations. The main findings are summarised below. The mean flow and the tides at Grahamstown and Adelaide are characteristically variable at planetary time scales. Wavelet spectral and multiresolution analyses reveal that the dominant planetary oscillation is the quasi-16-day oscillation. However, no apparent correlation in the 16-day waves of the mean flow, the diurnal tide and the semidiurnal tide was found. The short-term fluctuations were also investigated using complex demodulation and bispectral techniques and it was found that some of the observed variations in tides could be due to non-linear wave-wave interactions. The long-term trends of the mean flow and tides show patterns that are in broad agreement with theory, results from elsewhere (ground-based and satellite) and the results of the Global-Scale Wave Model and various models by Portnyagin and others. In general the mean flow, the amplitudes and phases of both tides were found to exhibit seasonal and interannual variations which are thought to be related to various factors including (i) changes in the atmospheric mean environment, (ii) thermotidal forcing (iii) gravity wave effects, (iv) planetary scale influence, (v) long-term (e.g. quasi-biennial oscillation) modulation, and (vi) solar activity. There are significant longitudinal differences in the dynamic structure between Grahamstown and Adelaide. More especially, Grahamstown tends to have stronger mean flow and tidal activity than Adelaide. For tides, these differences are thought to be partly due to nonmigrating tidal modes but, in general, migrating modes were found to be dominant.
- Full Text:
- Date Issued: 2002
Effects of Axial Ligands on the Photosensitising Properties of Silicon Octaphenoxyphthalocyanines
- Authors: Maree, Machiel David
- Date: 2002
- Subjects: Ligands , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4553 , http://hdl.handle.net/10962/d1018246
- Description: Various axially substituted Silicon octaphenoxyphthalocyanines were synthesised as potential photosensitisers in the photodynamic therapy of cancer. Conventional reflux reactions were used for synthesis as well as new microwave irradiation reactions, wherein the reaction times were decreased tenfold with a marginal increase in reaction yield and product purity. An interesting series of oligomeric (dimer to a nonamer) silicon octaphenoxyphthalocyanines were also successfully synthesised in a reaction similar to polymerisation reactions. These compounds were found to undergo an axial ligand transformation upon irradiation with red light (> 600 nm) in dimethylsulphoxide solution. All the ligands were transformed into the dihydroxy silicon octaphenoxyphthalocyanine with varying degrees of phototransformation quantum yields ranging in order from 10⁻³ to 10⁻⁵ depending on the axial ligand involved. During and after axial ligand transformations a photodegredation of the dihydroxy silicon octaphenoxy phthalocyanine was observed upon continued irradiation. The oligomers were found to undergo the same axial ligand transformation process with a phototransformation quantum yield of 10⁻⁵ The singlet oxygen quantum yields of the unaggregated monomeric silicon octaphenoxy phthalocyanines were all found to be approximately 0.2 with the exception of a compound with two (trihexyl)siloxy axial substituents that had a singlet oxygen quantum yield of approximately 0.4 in dimethylsulphoxide solutions. The oligomers showed a surprising trend of an increase in singlet oxygen quantum yield with an increase in phthalocyanine ring number up to the pentamer and then a dramatic decrease to the nonamer. The triplet quantum yield and triplet lifetime were determined by laser flash photolysis for selected compounds and no correlation was observed with any of these properties and the singlet oxygen quantum yields. These selected compounds all fluoresce and a very good correlation was found between the fluorescence lifetimes determined experimentally by laser photolysis and the Strickler-Berg equation for the non-aggregated compounds. Electrochemical measurements also indicate the importance of the axial ligands upon the behaviour of the phthalocyanines as cyclic voltammetric behaviour was determined by the nature of the axial ligand.
- Full Text:
- Date Issued: 2002
- Authors: Maree, Machiel David
- Date: 2002
- Subjects: Ligands , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4553 , http://hdl.handle.net/10962/d1018246
- Description: Various axially substituted Silicon octaphenoxyphthalocyanines were synthesised as potential photosensitisers in the photodynamic therapy of cancer. Conventional reflux reactions were used for synthesis as well as new microwave irradiation reactions, wherein the reaction times were decreased tenfold with a marginal increase in reaction yield and product purity. An interesting series of oligomeric (dimer to a nonamer) silicon octaphenoxyphthalocyanines were also successfully synthesised in a reaction similar to polymerisation reactions. These compounds were found to undergo an axial ligand transformation upon irradiation with red light (> 600 nm) in dimethylsulphoxide solution. All the ligands were transformed into the dihydroxy silicon octaphenoxyphthalocyanine with varying degrees of phototransformation quantum yields ranging in order from 10⁻³ to 10⁻⁵ depending on the axial ligand involved. During and after axial ligand transformations a photodegredation of the dihydroxy silicon octaphenoxy phthalocyanine was observed upon continued irradiation. The oligomers were found to undergo the same axial ligand transformation process with a phototransformation quantum yield of 10⁻⁵ The singlet oxygen quantum yields of the unaggregated monomeric silicon octaphenoxy phthalocyanines were all found to be approximately 0.2 with the exception of a compound with two (trihexyl)siloxy axial substituents that had a singlet oxygen quantum yield of approximately 0.4 in dimethylsulphoxide solutions. The oligomers showed a surprising trend of an increase in singlet oxygen quantum yield with an increase in phthalocyanine ring number up to the pentamer and then a dramatic decrease to the nonamer. The triplet quantum yield and triplet lifetime were determined by laser flash photolysis for selected compounds and no correlation was observed with any of these properties and the singlet oxygen quantum yields. These selected compounds all fluoresce and a very good correlation was found between the fluorescence lifetimes determined experimentally by laser photolysis and the Strickler-Berg equation for the non-aggregated compounds. Electrochemical measurements also indicate the importance of the axial ligands upon the behaviour of the phthalocyanines as cyclic voltammetric behaviour was determined by the nature of the axial ligand.
- Full Text:
- Date Issued: 2002
Effects of substituents on the photosensitizing and electrocatalytic properties of phthalocyanines
- Authors: Maree, Suzanne Elizabeth
- Date: 2002
- Subjects: Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4554 , http://hdl.handle.net/10962/d1018247
- Description: In this work a selection of octasubstituted phthalocyaninato Zinc, Ge(IV) and Sn(IV) complexes were synthesized for possible use in photodynamic therapy and their photochemistry, photophysics and electrochemistry studied. Third-generation complexes containing steroids, e.g. cholesterol and estrone, were synthesized to improve tumour selectivity. The zinc phthalocyanine complexes (ZnPc) showed that complexes containing electron-donating groups have higher photostability. Germanium phthalocyanine complexes (GePc) undergo phototransformation rather than direct photobleaching and the tin phthalocyanine complexes (SnPc) undergo photobleaching mediated by photoreduction of the phthalocyanine ring. Singlet oxygen production showed increased in the following order: GePc>SnPc>ZnPc. Triplet lifetimes of the GePc (168-340μs) are very similar to that of the ZnPc (197 - 366μs), but the triplet lifetimes of the SnPc are ten fold shorter (10 - 32μs ). Triplet quantum yields are higher for the GePc (0.20 - 0.50) and SnPc (0.08 - 0.45) than for the ZnPc (0.02 - 0.25). Fluorescence lifetimes of GePc ( 4.0 - 5.1 ns) are significantly longer than that of ZnPc (1.9 - 3.0 ns) and SnPc (0.2 - 0.4 ns). Fluorescence quantum yields decrease in the following order: GePc(0.21-0.31)>ZnPc(0.02-0.21)>SnPc(0.02- 0.06). Ring-substituted cobalt phthalocyanine complexes of the form CoPc(R)4 (R= NH2, N02, C(CH3)3, S03H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the Com/Co11 couple of the CoPc(R)4 complexes in acidic media and to the Con/Co1 couple in basic media. The catalytic current and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive and the currents increasing with increase in pH.
- Full Text:
- Date Issued: 2002
- Authors: Maree, Suzanne Elizabeth
- Date: 2002
- Subjects: Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4554 , http://hdl.handle.net/10962/d1018247
- Description: In this work a selection of octasubstituted phthalocyaninato Zinc, Ge(IV) and Sn(IV) complexes were synthesized for possible use in photodynamic therapy and their photochemistry, photophysics and electrochemistry studied. Third-generation complexes containing steroids, e.g. cholesterol and estrone, were synthesized to improve tumour selectivity. The zinc phthalocyanine complexes (ZnPc) showed that complexes containing electron-donating groups have higher photostability. Germanium phthalocyanine complexes (GePc) undergo phototransformation rather than direct photobleaching and the tin phthalocyanine complexes (SnPc) undergo photobleaching mediated by photoreduction of the phthalocyanine ring. Singlet oxygen production showed increased in the following order: GePc>SnPc>ZnPc. Triplet lifetimes of the GePc (168-340μs) are very similar to that of the ZnPc (197 - 366μs), but the triplet lifetimes of the SnPc are ten fold shorter (10 - 32μs ). Triplet quantum yields are higher for the GePc (0.20 - 0.50) and SnPc (0.08 - 0.45) than for the ZnPc (0.02 - 0.25). Fluorescence lifetimes of GePc ( 4.0 - 5.1 ns) are significantly longer than that of ZnPc (1.9 - 3.0 ns) and SnPc (0.2 - 0.4 ns). Fluorescence quantum yields decrease in the following order: GePc(0.21-0.31)>ZnPc(0.02-0.21)>SnPc(0.02- 0.06). Ring-substituted cobalt phthalocyanine complexes of the form CoPc(R)4 (R= NH2, N02, C(CH3)3, S03H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the Com/Co11 couple of the CoPc(R)4 complexes in acidic media and to the Con/Co1 couple in basic media. The catalytic current and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive and the currents increasing with increase in pH.
- Full Text:
- Date Issued: 2002
Non-governmental organizations, the state and the politics of rural development in Kenya with particular reference to Western Province
- Authors: Matanga, Frank Khachina
- Date: 2002
- Subjects: Non-governmental organizations -- Kenya , Rural development -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2803 , http://hdl.handle.net/10962/d1003013 , Non-governmental organizations -- Kenya , Rural development -- Kenya
- Description: In recent decades, Non-Governmental Organizations (NGOs) have increasingly taken on development and political roles in Africa. This has partly been attributed to the New Policy Agenda (NPA) mounted by the international donors. The NPA is predicated on neo-liberal thinking advocating for an enlarged development role for the private sector and a minimalist state. This relatively new shift in development thought has been motivated by the declining capacity of the African state to deliver development and guarantee a liberal political system. This study, therefore, set out to empirically examine whether NGOs are capable of effectively playing their new-found development and political roles. The study was based on Kenya with the Western Province constituting the core research area. The fact that the Kenyan state has been gradually disengaging from the development process has created a vacuum of which the NGOs have attempted to fill. Equally important has been the observation that, for the greater part of the post-colonial period, the state has been largely authoritarian and therefore prompting a segment of civil society to take on political roles in an effort to force it to liberalize and democratize. Urban NGOs in particular, have been the most confrontational to the state with some remarkable success. Unlike their urban counterparts, rural-based NGOs have tended to be more developmental and play a politics of collaboration with the state. Many of the latter NGOs, although playing a significant role in rural development, have been co-opted into patron-client networks. Factors that influence NGOs= posture towards the state include the nature of their leadership, the extent of their nternational connections, and the level of resources at their disposal. The study=s principal conclusion, is that, in as much as NGOs and overall civil society have provided a basis for development and opposition to the state, there is an urgent and growing need for them to shift from a position of dependency, whether domestic or international, to relative autonomy. Only then, will their contributions be sustainable in society.
- Full Text:
- Date Issued: 2002
- Authors: Matanga, Frank Khachina
- Date: 2002
- Subjects: Non-governmental organizations -- Kenya , Rural development -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2803 , http://hdl.handle.net/10962/d1003013 , Non-governmental organizations -- Kenya , Rural development -- Kenya
- Description: In recent decades, Non-Governmental Organizations (NGOs) have increasingly taken on development and political roles in Africa. This has partly been attributed to the New Policy Agenda (NPA) mounted by the international donors. The NPA is predicated on neo-liberal thinking advocating for an enlarged development role for the private sector and a minimalist state. This relatively new shift in development thought has been motivated by the declining capacity of the African state to deliver development and guarantee a liberal political system. This study, therefore, set out to empirically examine whether NGOs are capable of effectively playing their new-found development and political roles. The study was based on Kenya with the Western Province constituting the core research area. The fact that the Kenyan state has been gradually disengaging from the development process has created a vacuum of which the NGOs have attempted to fill. Equally important has been the observation that, for the greater part of the post-colonial period, the state has been largely authoritarian and therefore prompting a segment of civil society to take on political roles in an effort to force it to liberalize and democratize. Urban NGOs in particular, have been the most confrontational to the state with some remarkable success. Unlike their urban counterparts, rural-based NGOs have tended to be more developmental and play a politics of collaboration with the state. Many of the latter NGOs, although playing a significant role in rural development, have been co-opted into patron-client networks. Factors that influence NGOs= posture towards the state include the nature of their leadership, the extent of their nternational connections, and the level of resources at their disposal. The study=s principal conclusion, is that, in as much as NGOs and overall civil society have provided a basis for development and opposition to the state, there is an urgent and growing need for them to shift from a position of dependency, whether domestic or international, to relative autonomy. Only then, will their contributions be sustainable in society.
- Full Text:
- Date Issued: 2002
The political ecology of wildlife conservation in Kenya, 1895-1975
- Authors: Matheka, Reuben M
- Date: 2002
- Subjects: Wildlife conservation -- Kenya Environmental policy -- Kenya Wildlife conservation -- Political aspects -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2595 , http://hdl.handle.net/10962/d1007530
- Description: The study examines the development of wildlife conservation policy and practice in Kenya from 1895 to 1975. Started by the colonial state as part of its resource control programme, wildlife conservation in Kenya gradually became an important aspect of the country's economy chiefly because of its significance as the basis of a vibrant tourist industry. The conservation programme was also important to conservationists who viewed Kenya's wildlife as a heritage to humanity. Similarly, local communities, which were affected in various ways by wildlife conservation policies, had their own perceptions of the programme. All this led to the proliferation of groups whose interests were potentially conflicting. Wildlife conservation in Kenya during the period under examination was thus characterised by various struggles between interest groups such as conservationists, the state, and local communities. The struggles centred around such issues as the costs and benefits of conservation and were manifested through anti-conservation activities like the poaching of wild animals by dissatisfied groups. These struggles changed over time in line with social, economic, political, and ecological developments. International events/processes (such as the two world wars, economic booms/depressions, and decolonisation) triggered local processes which influenced conservationism either positively or negatively. Wildlife conservation in Kenya during the period under study was dynamic. The thesis challenges the myth of a monolithic 'colonial' wildlife policy often implied in many studies on the subject. The thesis also lays emphasis on the ecological basis of wildlife conservation while recognising the impact of social, political, and economic developments on the evolution of wildlife conservation policy and practice in Kenya. The country's 'geography' not only provided the foundation for conservation but also influenced the programme over time. Droughts, floods, army worm infestations, and other 'natural' occurrences interacted with social and economic changes, such as population growth and the development of capitalism, to shape conservation policy. The conservation programme was thus influenced by a complex interaction of a variety of factors.
- Full Text:
- Date Issued: 2002
- Authors: Matheka, Reuben M
- Date: 2002
- Subjects: Wildlife conservation -- Kenya Environmental policy -- Kenya Wildlife conservation -- Political aspects -- Kenya
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:2595 , http://hdl.handle.net/10962/d1007530
- Description: The study examines the development of wildlife conservation policy and practice in Kenya from 1895 to 1975. Started by the colonial state as part of its resource control programme, wildlife conservation in Kenya gradually became an important aspect of the country's economy chiefly because of its significance as the basis of a vibrant tourist industry. The conservation programme was also important to conservationists who viewed Kenya's wildlife as a heritage to humanity. Similarly, local communities, which were affected in various ways by wildlife conservation policies, had their own perceptions of the programme. All this led to the proliferation of groups whose interests were potentially conflicting. Wildlife conservation in Kenya during the period under examination was thus characterised by various struggles between interest groups such as conservationists, the state, and local communities. The struggles centred around such issues as the costs and benefits of conservation and were manifested through anti-conservation activities like the poaching of wild animals by dissatisfied groups. These struggles changed over time in line with social, economic, political, and ecological developments. International events/processes (such as the two world wars, economic booms/depressions, and decolonisation) triggered local processes which influenced conservationism either positively or negatively. Wildlife conservation in Kenya during the period under study was dynamic. The thesis challenges the myth of a monolithic 'colonial' wildlife policy often implied in many studies on the subject. The thesis also lays emphasis on the ecological basis of wildlife conservation while recognising the impact of social, political, and economic developments on the evolution of wildlife conservation policy and practice in Kenya. The country's 'geography' not only provided the foundation for conservation but also influenced the programme over time. Droughts, floods, army worm infestations, and other 'natural' occurrences interacted with social and economic changes, such as population growth and the development of capitalism, to shape conservation policy. The conservation programme was thus influenced by a complex interaction of a variety of factors.
- Full Text:
- Date Issued: 2002
Continuity and generalized continuity in dynamics and other applications
- Authors: Mimna, Roy Allan
- Date: 2002
- Subjects: Topological dynamics -- Research Dynamics -- Mathematical models -- Research Perturbation (Mathematics) Attractors (Mathematics) Baire classes Mathematics -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5404 , http://hdl.handle.net/10962/d1005218
- Description: The topological dynamics of continuous and noncontinuous dynamical systems are investigated. Various definitions of chaos are studied, as well as notions of stability. Results are obtained on asymptotically stable sets and the perturbation stability of such sets. The primary focus is on the traditional point sets of topological dynamics, including the chain recurrent set, omega-limit sets and attractors. The basic setting is that of a continuous function on a compact metric space, sometimes with additional properties on the space. The investigation includes results on the dynamical properties of typical continuous functions in the sense of Baire category. Results are also developed concerning dynamical systems involving quasi-continuous functions. An invariance property for the omega-limit sets of such functions is given. Omega-limit sets are characterized for Riemann integrable derivatives and derivatiyes which are continuous almost everywhere. Techniques used in the investigation and formulation of results include finding theorems which relate the rather disparate notions of dynamical properties and generalized continuity. In addition to dynamical systems, numerous other applications of generalized continuity are imoestigated. Techniques used include application of the Baire Category Theorem and the notion of semi-closure. For example, results are formulated concerning functions determined by dense sets, including separately continuous functions, thus generalizing the classical result for continuous functions on dense subsets of the domain. The uniform boundedness theorem is extended to functions which are not necessarily continuous, including various derivatives. The closed graph theorem is strictly generalized in two separate ways, and applications are presented using these generalizations. An invariance property of separately continuous functions is given. Cluster sets are studied in connection with separate continuity, and various results are presented concerning locally bounded functions.
- Full Text:
- Date Issued: 2002
- Authors: Mimna, Roy Allan
- Date: 2002
- Subjects: Topological dynamics -- Research Dynamics -- Mathematical models -- Research Perturbation (Mathematics) Attractors (Mathematics) Baire classes Mathematics -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5404 , http://hdl.handle.net/10962/d1005218
- Description: The topological dynamics of continuous and noncontinuous dynamical systems are investigated. Various definitions of chaos are studied, as well as notions of stability. Results are obtained on asymptotically stable sets and the perturbation stability of such sets. The primary focus is on the traditional point sets of topological dynamics, including the chain recurrent set, omega-limit sets and attractors. The basic setting is that of a continuous function on a compact metric space, sometimes with additional properties on the space. The investigation includes results on the dynamical properties of typical continuous functions in the sense of Baire category. Results are also developed concerning dynamical systems involving quasi-continuous functions. An invariance property for the omega-limit sets of such functions is given. Omega-limit sets are characterized for Riemann integrable derivatives and derivatiyes which are continuous almost everywhere. Techniques used in the investigation and formulation of results include finding theorems which relate the rather disparate notions of dynamical properties and generalized continuity. In addition to dynamical systems, numerous other applications of generalized continuity are imoestigated. Techniques used include application of the Baire Category Theorem and the notion of semi-closure. For example, results are formulated concerning functions determined by dense sets, including separately continuous functions, thus generalizing the classical result for continuous functions on dense subsets of the domain. The uniform boundedness theorem is extended to functions which are not necessarily continuous, including various derivatives. The closed graph theorem is strictly generalized in two separate ways, and applications are presented using these generalizations. An invariance property of separately continuous functions is given. Cluster sets are studied in connection with separate continuity, and various results are presented concerning locally bounded functions.
- Full Text:
- Date Issued: 2002
Chemical studies of selected chromone derivatives
- Authors: Nchinda, Aloysius Tchangwe
- Date: 2002
- Subjects: Heterocyclic compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4434 , http://hdl.handle.net/10962/d1007442
- Description: This investigation has been geared towards several aspects of chromone chemistry. Selected 2-(N,N-dimethylarnino)chromones have been synthesized via 2-hydroxyacetophenone boron difluoride complex intermediates, and potentiometric analysis of these compounds in ethanolwater has been used to determine the influence of substituents on their basicity. The pKa values have been found to lie within a narrow range (1.92 - 2.52), and the observed substituent effects have been rationalized with the aid of semi-empirical and ab initio molecular orbital calculations. An efficient route has been developed for the synthesis of the naturally-occurring chromone, "granulosin" [7,8-(methylenedioxy)-2-propylchromone], and several C-2 side chain analogues in good yields, by condensing 2'-hydroxy-3',4'-(methylenedioxy)acetophenone with a range of ethyl carboxylate esters. These compounds show significant cytotoxic activity against the brine shrimp, Artemia salina, and two of them, the 2-ethyl and 2-benzyl derivatives also show 100% activity as pesticides on Beet army worms (BAW). Another naturally-occurring chromone derivative, 5-hydroxy-2-isopropyl-7-methoxychromone, and four C-2 side chain analogues have been prepared in moderate yields. These compounds also show significant cytotoxic activity against the brine shrimp, Artemia salina, and it is apparent that the presence of the hydroxyl group at C-5 is critical for such activity. The electronimpact mass spectra of both series of chromone derivatives have been investigated, permitting the elucidation of characteristic fragmentation patterns. In work directed towards the synthesis of potential HIV -1 protease inhibitors, five novel chromone-containing analogues of the clinically useful drug, ritonavir, have been synthesized. The design strategy has involved the coupling of substituted chromone-2- carboxylic acids with a specially prepared, hydroxyethylene dipeptide isostere to afford ritonavir analogues containing chromone termini. An interactive docking procedure has been used to explore the docking of ritonavir and the novel chromone-containing analogues into ' the active site of the enzyme, and has indicated the capacity of the ritonavir analogues to form hydrogen-bonds with the HJV-l enzyme receptor. Various substituted cbromone-3-carbaldehydes, which have been synthesized from the corresponding o-hyclroxyacetophenones using Vilsmeier-Haack methodology, have been examined as substrates for Morita-Baylis-Hillman reactions, using 3-hyclroxyquinuclidine as the catalyst and arcylonitrile and methyl acrylate as the activated alkenes. Optimization of the reaction conditions has permitted efficient conversion of the cbromone-3-carbaldehydes to the Morita-Baylis-Hillman products and, in some cases, dimeric products, within 24 h. Heating of the Morita-Baylis-Hillman products, arising from reactions with methyl acrylate, at 80 ºC for 3 h in the presence of DABCO as catalyst, has been shown to effect transformation to the corresponding dimers in good yield.
- Full Text:
- Date Issued: 2002
- Authors: Nchinda, Aloysius Tchangwe
- Date: 2002
- Subjects: Heterocyclic compounds
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4434 , http://hdl.handle.net/10962/d1007442
- Description: This investigation has been geared towards several aspects of chromone chemistry. Selected 2-(N,N-dimethylarnino)chromones have been synthesized via 2-hydroxyacetophenone boron difluoride complex intermediates, and potentiometric analysis of these compounds in ethanolwater has been used to determine the influence of substituents on their basicity. The pKa values have been found to lie within a narrow range (1.92 - 2.52), and the observed substituent effects have been rationalized with the aid of semi-empirical and ab initio molecular orbital calculations. An efficient route has been developed for the synthesis of the naturally-occurring chromone, "granulosin" [7,8-(methylenedioxy)-2-propylchromone], and several C-2 side chain analogues in good yields, by condensing 2'-hydroxy-3',4'-(methylenedioxy)acetophenone with a range of ethyl carboxylate esters. These compounds show significant cytotoxic activity against the brine shrimp, Artemia salina, and two of them, the 2-ethyl and 2-benzyl derivatives also show 100% activity as pesticides on Beet army worms (BAW). Another naturally-occurring chromone derivative, 5-hydroxy-2-isopropyl-7-methoxychromone, and four C-2 side chain analogues have been prepared in moderate yields. These compounds also show significant cytotoxic activity against the brine shrimp, Artemia salina, and it is apparent that the presence of the hydroxyl group at C-5 is critical for such activity. The electronimpact mass spectra of both series of chromone derivatives have been investigated, permitting the elucidation of characteristic fragmentation patterns. In work directed towards the synthesis of potential HIV -1 protease inhibitors, five novel chromone-containing analogues of the clinically useful drug, ritonavir, have been synthesized. The design strategy has involved the coupling of substituted chromone-2- carboxylic acids with a specially prepared, hydroxyethylene dipeptide isostere to afford ritonavir analogues containing chromone termini. An interactive docking procedure has been used to explore the docking of ritonavir and the novel chromone-containing analogues into ' the active site of the enzyme, and has indicated the capacity of the ritonavir analogues to form hydrogen-bonds with the HJV-l enzyme receptor. Various substituted cbromone-3-carbaldehydes, which have been synthesized from the corresponding o-hyclroxyacetophenones using Vilsmeier-Haack methodology, have been examined as substrates for Morita-Baylis-Hillman reactions, using 3-hyclroxyquinuclidine as the catalyst and arcylonitrile and methyl acrylate as the activated alkenes. Optimization of the reaction conditions has permitted efficient conversion of the cbromone-3-carbaldehydes to the Morita-Baylis-Hillman products and, in some cases, dimeric products, within 24 h. Heating of the Morita-Baylis-Hillman products, arising from reactions with methyl acrylate, at 80 ºC for 3 h in the presence of DABCO as catalyst, has been shown to effect transformation to the corresponding dimers in good yield.
- Full Text:
- Date Issued: 2002
Genetic characterization of conspecific populations of Tilapia Sparrmanii (A.Smith 1840) in the dolomitic sinkholes and springs of the North-West Province (South Africa), and their comparison to Tilapia Guinasana (Trewavas 1936)
- Authors: Nxomani, Clifford David
- Date: 2002
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4079 , http://hdl.handle.net/10962/d1007452
- Description: This study was undertaken to investigate the genetic relationships of allopatric populations of the cichlid fish, Tilapia sparrmanii (A. Smith 1840) inhabiting the sinkholes and springs of the North West Province, South Africa. It also examined the genetic relationships of T sparrmanii to its polychromatic sister species, Tilapia guinasana (Trewavas 1936) which is endemic to the Guinas sinkhole in Namibia. Finally, the study investigated whether there is a genetic basis for T guinasana's colour polymorphism. The research was prompted by the concern of conservation authorities about the possible loss of unique fauna given the high demand for use of the subterranean waters for agricultural, domestic and industrial purposes. Such demands have the potential to drain these habitats. Further concerns related to habitat destruction and the introduction of alien species in the ecosystems inhabited by both fish species. Three approaches were adopted in attempting to answer the above questions. First was the investigation of Sodium dodecylsulphate (SDS)-Polyacrylamide Gel Electrophoresis (PAGE) of total cellular proteins as a fast and relatively inexpensive indicator of genetic relatedness between the fish populations. Secondly, genetic differentiation between the T sparrmanii populations and its relationship to T guinasana were assayed using restriction endonuclease analysis of Polymerase Chain Reaction (PCR)-amplified regions of the cytochrome b gene and the d-Ioop of mitochondrial DNA, coupled with Temperature Gradient Gel Electrophoresis (TGGE) analysis of the same regions. The third approach involved the use of Random Amplified Polymorphic DNA (RAPD) fingerprinting of the populations ofT sparrmanii as an indicator of genetic differentiation between them. RAPD fingerprinting was further used to investigate the genetic relationships between T sparrmanii and T guinasana and to probe the genetic basis of the polychromatism of the latter. SDS-PAGE did not reveal any genetic differentiation between the T sparrmanii populations, nor could the analysis detect variation within them. It however clearly distinguished at a species level between T sparrmanii and T guinasana as well as between these and other fish species, thus indicating its possible utility as an indicator of genetic relatedness at a species level. Mitochondrial studies employing the Restriction Fragment Length Polymorphism (RFLP) of Polymerase Chain Reaction (PCR)-amplified cytochrome b (1.1 kb) and d-Ioop regions (0.9 kb) with six and five restriction enzymes respectively, failed to reveal genetic differences within and between the allopatric populations. TGGE of500 bp of the d-Ioop and 400 bp of the 12sRNA PCR-amplified fragments did not reveal any differences between the populations of T. sparrmanii, nor did the analysis reveal any differences between T. sparrmanii and T. guinasana. The lack of differentiation between the T. sparrmanii populations by these mitochondrial Dna analysis techniques, despite habitat fragmentation, indicated a recent origin of the populations from a common ancestral population. Failure to distinguish between T. sparrmanii and T. guinasana may be related to the sensitivity of the techniques utilized. RAPD fingerprinting analysis indicated that the populations are genetically differentiated from each other. Using a measure of coefficient of variation, the population with the highest variation was the Wondergat population (13.99%), followed by the Klerkskraal popUlation (8.29%), the Malmani and Marico Oog populations (each with 5.88%) and the least variation (4.95 and 4.83%) was with the Amalinda and Molopo Oog populations respectively. This high degree of intra population similarity points to the fact that this differentiation is still confined within the limits of con specificity. The genetic distances between all of the T. sparrmanii populations across all primers ranged from 0.09 to 0.234 and averaged 0.146, a value that falls in the upper end of conspecific population differentiation. Such results indicate populational sub-division below the species level. RAPD fingerprinting therefore proved more sensitive than protein or mitochondrial studies. The differentiation it detected between the populations is a reflection of their adaptation to local conditions of the unique ecosystems they inhabit. A comparison with a subset of primers between T. guinasana and T. sparrmanii confirmed the separate species status of the former from the latter. The mean genetic distance between the T. sparrmanii populations was 0.136, compared to that between T. sparrmanii and T. guinasana which was found to be 0.374. Statistical analysis of the difference between the mean genetic distances indicated significance with 95% confidence. The polychromatism of T guinasana was investigated to determine whether there were significant differences between its five colour morphs. RAPD fingerprinting indicated with 95% confidence that there were significant differences between the colour forms based on the genetic distances computed between them. These genetic differences appeared to correlate with the observed assortative mating between the colour forms of the species. The manifestation of the polychromatism at sexual maturity in T guinasana probably indicates that colouration plays an important role in the breeding process. The genetic uniqueness shown here between the populations of T sparrmanii and the colour forms of T guinasana indicate for protective measures to be put in place if the genetic resources of the isolated fish populations are to be preserved. These must be coupled with a thorough assessment of the temporal and spatial distribution of genetic variability of the populations as a guide to a long-term management strategy for the fish populations and the ecosystems they inhabit. This study therefore has shown that the allopatric populations of T sparrmanii in the sinkholes and springs of the North-West Province are genetically unique, as well as show that the colour forms of T guinasana are genetically distinct.
- Full Text:
- Date Issued: 2002
- Authors: Nxomani, Clifford David
- Date: 2002
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4079 , http://hdl.handle.net/10962/d1007452
- Description: This study was undertaken to investigate the genetic relationships of allopatric populations of the cichlid fish, Tilapia sparrmanii (A. Smith 1840) inhabiting the sinkholes and springs of the North West Province, South Africa. It also examined the genetic relationships of T sparrmanii to its polychromatic sister species, Tilapia guinasana (Trewavas 1936) which is endemic to the Guinas sinkhole in Namibia. Finally, the study investigated whether there is a genetic basis for T guinasana's colour polymorphism. The research was prompted by the concern of conservation authorities about the possible loss of unique fauna given the high demand for use of the subterranean waters for agricultural, domestic and industrial purposes. Such demands have the potential to drain these habitats. Further concerns related to habitat destruction and the introduction of alien species in the ecosystems inhabited by both fish species. Three approaches were adopted in attempting to answer the above questions. First was the investigation of Sodium dodecylsulphate (SDS)-Polyacrylamide Gel Electrophoresis (PAGE) of total cellular proteins as a fast and relatively inexpensive indicator of genetic relatedness between the fish populations. Secondly, genetic differentiation between the T sparrmanii populations and its relationship to T guinasana were assayed using restriction endonuclease analysis of Polymerase Chain Reaction (PCR)-amplified regions of the cytochrome b gene and the d-Ioop of mitochondrial DNA, coupled with Temperature Gradient Gel Electrophoresis (TGGE) analysis of the same regions. The third approach involved the use of Random Amplified Polymorphic DNA (RAPD) fingerprinting of the populations ofT sparrmanii as an indicator of genetic differentiation between them. RAPD fingerprinting was further used to investigate the genetic relationships between T sparrmanii and T guinasana and to probe the genetic basis of the polychromatism of the latter. SDS-PAGE did not reveal any genetic differentiation between the T sparrmanii populations, nor could the analysis detect variation within them. It however clearly distinguished at a species level between T sparrmanii and T guinasana as well as between these and other fish species, thus indicating its possible utility as an indicator of genetic relatedness at a species level. Mitochondrial studies employing the Restriction Fragment Length Polymorphism (RFLP) of Polymerase Chain Reaction (PCR)-amplified cytochrome b (1.1 kb) and d-Ioop regions (0.9 kb) with six and five restriction enzymes respectively, failed to reveal genetic differences within and between the allopatric populations. TGGE of500 bp of the d-Ioop and 400 bp of the 12sRNA PCR-amplified fragments did not reveal any differences between the populations of T. sparrmanii, nor did the analysis reveal any differences between T. sparrmanii and T. guinasana. The lack of differentiation between the T. sparrmanii populations by these mitochondrial Dna analysis techniques, despite habitat fragmentation, indicated a recent origin of the populations from a common ancestral population. Failure to distinguish between T. sparrmanii and T. guinasana may be related to the sensitivity of the techniques utilized. RAPD fingerprinting analysis indicated that the populations are genetically differentiated from each other. Using a measure of coefficient of variation, the population with the highest variation was the Wondergat population (13.99%), followed by the Klerkskraal popUlation (8.29%), the Malmani and Marico Oog populations (each with 5.88%) and the least variation (4.95 and 4.83%) was with the Amalinda and Molopo Oog populations respectively. This high degree of intra population similarity points to the fact that this differentiation is still confined within the limits of con specificity. The genetic distances between all of the T. sparrmanii populations across all primers ranged from 0.09 to 0.234 and averaged 0.146, a value that falls in the upper end of conspecific population differentiation. Such results indicate populational sub-division below the species level. RAPD fingerprinting therefore proved more sensitive than protein or mitochondrial studies. The differentiation it detected between the populations is a reflection of their adaptation to local conditions of the unique ecosystems they inhabit. A comparison with a subset of primers between T. guinasana and T. sparrmanii confirmed the separate species status of the former from the latter. The mean genetic distance between the T. sparrmanii populations was 0.136, compared to that between T. sparrmanii and T. guinasana which was found to be 0.374. Statistical analysis of the difference between the mean genetic distances indicated significance with 95% confidence. The polychromatism of T guinasana was investigated to determine whether there were significant differences between its five colour morphs. RAPD fingerprinting indicated with 95% confidence that there were significant differences between the colour forms based on the genetic distances computed between them. These genetic differences appeared to correlate with the observed assortative mating between the colour forms of the species. The manifestation of the polychromatism at sexual maturity in T guinasana probably indicates that colouration plays an important role in the breeding process. The genetic uniqueness shown here between the populations of T sparrmanii and the colour forms of T guinasana indicate for protective measures to be put in place if the genetic resources of the isolated fish populations are to be preserved. These must be coupled with a thorough assessment of the temporal and spatial distribution of genetic variability of the populations as a guide to a long-term management strategy for the fish populations and the ecosystems they inhabit. This study therefore has shown that the allopatric populations of T sparrmanii in the sinkholes and springs of the North-West Province are genetically unique, as well as show that the colour forms of T guinasana are genetically distinct.
- Full Text:
- Date Issued: 2002
Detection of neurotransmitters using metallophthalocyanines as electrocatalysts
- Authors: Oni, Joshua Idowu
- Date: 2002
- Subjects: Neurotransmitters Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4435 , http://hdl.handle.net/10962/d1007470
- Description: Some metallophthalocyanine complexes were synthesized and their catalytic activities towards the detection and quantification of the neurotransmitters dopamine, serotonin and histamine were investigated. The study of the possible interaction between these transmitter substances and the metallophthalocyanine complexes was undertaken. Dopamine, serotonin and histamine formed complexes with Iron (II) tetrasulfophthalocyanine. The rate and equilibrium constants obtained for the coordination are in the range of values reported in the literature for ligand coordination to iron phthalocyanine complexes. Carbon paste electrodes of millimetric diameters modified with Iron (II) tetrasulfophthalocyanine exhibited good electro catalytic activity towards the detection and analysis of dopamine and serotonin while at the same time eliminated the problem of interference posed by ascorbic acid in the electrochemical analysis of neurotransmitters. A detection limit of the order of 10-6 mol dm-3 was obtained for both dopamine and serotonin at the modified electrodes. Carbon paste ultra micro electrodes modified with iron (II) tetrasulfophthalocyanine were also used for the detection of dopamine and serotonin as well as the simultaneous determination of dopamine and ascorbic acid in a mixture. The detection limit obtained for dopamine at the ultra microelectrode was 4.2xlO-7 mol dm-3 The electrode kinetics of vitamin BI as well as the stability of the electrode towards its determination was improved upon by modifying carbon paste electrodes with manganese phthalocyanine. The modified electrodes were used for the analysis of vitamin BI in tablets.
- Full Text:
- Date Issued: 2002
- Authors: Oni, Joshua Idowu
- Date: 2002
- Subjects: Neurotransmitters Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4435 , http://hdl.handle.net/10962/d1007470
- Description: Some metallophthalocyanine complexes were synthesized and their catalytic activities towards the detection and quantification of the neurotransmitters dopamine, serotonin and histamine were investigated. The study of the possible interaction between these transmitter substances and the metallophthalocyanine complexes was undertaken. Dopamine, serotonin and histamine formed complexes with Iron (II) tetrasulfophthalocyanine. The rate and equilibrium constants obtained for the coordination are in the range of values reported in the literature for ligand coordination to iron phthalocyanine complexes. Carbon paste electrodes of millimetric diameters modified with Iron (II) tetrasulfophthalocyanine exhibited good electro catalytic activity towards the detection and analysis of dopamine and serotonin while at the same time eliminated the problem of interference posed by ascorbic acid in the electrochemical analysis of neurotransmitters. A detection limit of the order of 10-6 mol dm-3 was obtained for both dopamine and serotonin at the modified electrodes. Carbon paste ultra micro electrodes modified with iron (II) tetrasulfophthalocyanine were also used for the detection of dopamine and serotonin as well as the simultaneous determination of dopamine and ascorbic acid in a mixture. The detection limit obtained for dopamine at the ultra microelectrode was 4.2xlO-7 mol dm-3 The electrode kinetics of vitamin BI as well as the stability of the electrode towards its determination was improved upon by modifying carbon paste electrodes with manganese phthalocyanine. The modified electrodes were used for the analysis of vitamin BI in tablets.
- Full Text:
- Date Issued: 2002
Reproductive conflicts in honeybee colonies
- Pirk, Christian Walter Werner
- Authors: Pirk, Christian Walter Werner
- Date: 2002
- Subjects: Honeybee -- Reproduction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5755 , http://hdl.handle.net/10962/d1005443
- Description: In advanced eusocial hymenopteran societies workers have ovaries and can lay eggs, but are unable to mate. Workers are more related to their own offspring than to every other member of the colony. So worker reproduction contains both worker-worker and worker-queen conflict. The queen- worker conflict is discussed elsewhere, but if the queen mates with more than two males, worker policing should be selected to lower potential conflicts. However in the Cape honeybee it was predicted that worker policing is absent or less expressed than in other honeybee subspecies, because workers produce female offspring thelytokously. So laying workers and their offspring are nearly genetically identical, which results in the fact that other workers are as related to workers derived from eggs laid by the queen as laid by a worker. However, worker reproduction may be costly and therefore worker policing could be an evolutionary adaptation in the Cape honeybee to lower the costs derived from laying worker activity. Indeed, Cape honeybee colonies show efficient egg removal behaviour, suggesting that other factors like colony efficiency could favour egg removal behaviour. Since egg removal behaviour is a colony phenomenon, factors that affect colony performance could also affect egg removal behaviour. Egg removal behaviour was considerably affected by environmental changes, indicating that other tasks have a higher priority than egg removal behaviour. Thousands of queenright colonies of the neighbouring subspecies (A. m. scutellata) were taken over by laying A. m. capensis workers, showing that A. m. capensis workers are facultative social parasites. These observations strongly indicate that laying workers of A. m. capensis are able to evade worker policing and the inhibitory effects of the queen pheromones, but what potential strategies could these laying workers use to increase the survival of their eggs and evade the queen? On the one hand, egg removal behaviour is variable. One behavioural strategy of laying workers to achieve successful reproduction could be that they lay during periods with low egg removal behaviour. On the other hand, the inhibitory effect of the queen’s pheromones diminishes with distance. Maybe the level of egg removal also depends, like the inhibitory effect of the queen pheromones, on the distance from the queen. Indeed, further away from the queen the effect of the queen pheromone and the level of egg removal is reduced, making successful worker reproduction possible. In both subspecies, A. m. capensis and A. m. scutellata, egg removal behaviour is reduced further away from the queen. In the case of A. m. scutellata egg removal is lacking further away from the queen. This explains why colonies of scutellata are so prone to takeovers by laying Cape honeybee workers. One question in the context of parasitic Cape honeybees is how they manage to get into the host colony. One way could be that they get into the colonies during a natural colony merger which is common in African bees. Two unrelated colonies merged and it took them only 24 hours to show effective integration. Because both colonies are unrelated, the potential reproductive conflict among workers should be more strongly expressed than in a normal colony, which is not the result of a merger. Therefore, the effect of nestmate recognition for eggs on the egg removal behaviour was investigated. The results suggest that workers recognise the origin of an egg and that the standard policing experiments overestimate the level of egg removal and only represent relative values. Moreover, the results show that colony specific components on the eggs are more important than a postulated queen egg marking pheromone. Finally, for the first time empirical evidence from a population of the parasitic laying Cape honeybee workers, invading thousands of colonies of A. m. scutellata in northern South Africa, for a short-sighted selection theory is presented.
- Full Text:
- Date Issued: 2002
- Authors: Pirk, Christian Walter Werner
- Date: 2002
- Subjects: Honeybee -- Reproduction
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5755 , http://hdl.handle.net/10962/d1005443
- Description: In advanced eusocial hymenopteran societies workers have ovaries and can lay eggs, but are unable to mate. Workers are more related to their own offspring than to every other member of the colony. So worker reproduction contains both worker-worker and worker-queen conflict. The queen- worker conflict is discussed elsewhere, but if the queen mates with more than two males, worker policing should be selected to lower potential conflicts. However in the Cape honeybee it was predicted that worker policing is absent or less expressed than in other honeybee subspecies, because workers produce female offspring thelytokously. So laying workers and their offspring are nearly genetically identical, which results in the fact that other workers are as related to workers derived from eggs laid by the queen as laid by a worker. However, worker reproduction may be costly and therefore worker policing could be an evolutionary adaptation in the Cape honeybee to lower the costs derived from laying worker activity. Indeed, Cape honeybee colonies show efficient egg removal behaviour, suggesting that other factors like colony efficiency could favour egg removal behaviour. Since egg removal behaviour is a colony phenomenon, factors that affect colony performance could also affect egg removal behaviour. Egg removal behaviour was considerably affected by environmental changes, indicating that other tasks have a higher priority than egg removal behaviour. Thousands of queenright colonies of the neighbouring subspecies (A. m. scutellata) were taken over by laying A. m. capensis workers, showing that A. m. capensis workers are facultative social parasites. These observations strongly indicate that laying workers of A. m. capensis are able to evade worker policing and the inhibitory effects of the queen pheromones, but what potential strategies could these laying workers use to increase the survival of their eggs and evade the queen? On the one hand, egg removal behaviour is variable. One behavioural strategy of laying workers to achieve successful reproduction could be that they lay during periods with low egg removal behaviour. On the other hand, the inhibitory effect of the queen’s pheromones diminishes with distance. Maybe the level of egg removal also depends, like the inhibitory effect of the queen pheromones, on the distance from the queen. Indeed, further away from the queen the effect of the queen pheromone and the level of egg removal is reduced, making successful worker reproduction possible. In both subspecies, A. m. capensis and A. m. scutellata, egg removal behaviour is reduced further away from the queen. In the case of A. m. scutellata egg removal is lacking further away from the queen. This explains why colonies of scutellata are so prone to takeovers by laying Cape honeybee workers. One question in the context of parasitic Cape honeybees is how they manage to get into the host colony. One way could be that they get into the colonies during a natural colony merger which is common in African bees. Two unrelated colonies merged and it took them only 24 hours to show effective integration. Because both colonies are unrelated, the potential reproductive conflict among workers should be more strongly expressed than in a normal colony, which is not the result of a merger. Therefore, the effect of nestmate recognition for eggs on the egg removal behaviour was investigated. The results suggest that workers recognise the origin of an egg and that the standard policing experiments overestimate the level of egg removal and only represent relative values. Moreover, the results show that colony specific components on the eggs are more important than a postulated queen egg marking pheromone. Finally, for the first time empirical evidence from a population of the parasitic laying Cape honeybee workers, invading thousands of colonies of A. m. scutellata in northern South Africa, for a short-sighted selection theory is presented.
- Full Text:
- Date Issued: 2002
RADGIS - an improved architecture for runtime-extensible, distributed GIS applications
- Authors: Preston, Richard Michael
- Date: 2002
- Subjects: Geographic information systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4626 , http://hdl.handle.net/10962/d1006497
- Description: A number of GIS architectures and technologies have emerged recently to facilitate the visualisation and processing of geospatial data over the Web. The work presented in this dissertation builds on these efforts and undertakes to overcome some of the major problems with traditional GIS client architectures, including application bloat, lack of customisability, and lack of interoperability between GIS products. In this dissertation we describe how a new client-side GIS architecture was developed and implemented as a proof-of-concept application called RADGIS, which is based on open standards and emerging distributed component-based software paradigms. RADGIS reflects the current trend in development focus from Web browser-based applications to customised clients, based on open standards, that make use of distributed Web services. While much attention has been paid to exposing data on the Web, there is growing momentum towards providing “value-added” services. A good example of this is the tremendous industry interest in the provision of location-based services, which has been discussed as a special use-case of our RADGIS architecture. Thus, in the near future client applications will not simply be used to access data transparently, but will also become facilitators for the location-transparent invocation of local and remote services. This flexible architecture will ensure that data can be stored and processed independently of the location of the client that wishes to view or interact with it. Our RADGIS application enables content developers and end-users to create and/or customise GIS applications dynamically at runtime through the incorporation of GIS services. This ensures that the client application has the flexibility to withstand changing levels of expertise or user requirements. These GIS services are implemented as components that execute locally on the client machine, or as remote CORBA Objects or EJBs. Assembly and deployment of these components is achieved using a specialised XML descriptor. This XML descriptor is written using a markup language that we developed specifically for this purpose, called DGCML, which contains deployment information, as well as a GUI specification and links to an XML-based help system that can be merged with the RADGIS client application’s existing help system. Thus, no additional requirements are imposed on object developers by the RADGIS architecture, i.e. there is no need to rewrite existing objects since DGCML acts as a runtime-customisable wrapper, allowing existing objects to be utilised by RADGIS. While the focus of this thesis has been on overcoming the above-mentioned problems with traditional GIS applications, the work described here can also be applied in a much broader context, especially in the development of highly customisable client applications that are able to integrate Web services at runtime.
- Full Text:
- Date Issued: 2002
- Authors: Preston, Richard Michael
- Date: 2002
- Subjects: Geographic information systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4626 , http://hdl.handle.net/10962/d1006497
- Description: A number of GIS architectures and technologies have emerged recently to facilitate the visualisation and processing of geospatial data over the Web. The work presented in this dissertation builds on these efforts and undertakes to overcome some of the major problems with traditional GIS client architectures, including application bloat, lack of customisability, and lack of interoperability between GIS products. In this dissertation we describe how a new client-side GIS architecture was developed and implemented as a proof-of-concept application called RADGIS, which is based on open standards and emerging distributed component-based software paradigms. RADGIS reflects the current trend in development focus from Web browser-based applications to customised clients, based on open standards, that make use of distributed Web services. While much attention has been paid to exposing data on the Web, there is growing momentum towards providing “value-added” services. A good example of this is the tremendous industry interest in the provision of location-based services, which has been discussed as a special use-case of our RADGIS architecture. Thus, in the near future client applications will not simply be used to access data transparently, but will also become facilitators for the location-transparent invocation of local and remote services. This flexible architecture will ensure that data can be stored and processed independently of the location of the client that wishes to view or interact with it. Our RADGIS application enables content developers and end-users to create and/or customise GIS applications dynamically at runtime through the incorporation of GIS services. This ensures that the client application has the flexibility to withstand changing levels of expertise or user requirements. These GIS services are implemented as components that execute locally on the client machine, or as remote CORBA Objects or EJBs. Assembly and deployment of these components is achieved using a specialised XML descriptor. This XML descriptor is written using a markup language that we developed specifically for this purpose, called DGCML, which contains deployment information, as well as a GUI specification and links to an XML-based help system that can be merged with the RADGIS client application’s existing help system. Thus, no additional requirements are imposed on object developers by the RADGIS architecture, i.e. there is no need to rewrite existing objects since DGCML acts as a runtime-customisable wrapper, allowing existing objects to be utilised by RADGIS. While the focus of this thesis has been on overcoming the above-mentioned problems with traditional GIS applications, the work described here can also be applied in a much broader context, especially in the development of highly customisable client applications that are able to integrate Web services at runtime.
- Full Text:
- Date Issued: 2002
The ecophysiology of selected coastal dune pioneer plants of the Eastern Cape
- Authors: Ripley, B S
- Date: 2002
- Subjects: Sand dune plants -- South Africa -- Eastern Cape Sand dune ecology -- South Africa -- Eastern Cape Sand dune plants -- Ecophysiology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4222 , http://hdl.handle.net/10962/d1003791
- Description: Understanding the mechanisms and adaptations that allow only certain species to thrive in the potentially stressful foredune environment requires a knowledge of the basic ecophysiology of foredune species. Ecophysiological measurements were conducted on the foredune pioneer species Arctotheca populifolia (Berg.) Norl., Ipomoea pes-caprae(L.) R. Br. and Scaevola plumieri (L.) Vahl. and showed significant differences among species with respect to the physiology associated with biomass production, water and nutrient relations. Differences related to CO₂ assimilation included differences in photosynthetic and respiratory rates, susceptibility to light stress and leaf and stem non-structural carbohydrate concentrations. These resulted in differences in primary production rates of shoots. Mechanisms leading to the differences in CO₂ assimilation among species included differences in stomatal behaviour, carboxylation efficiencies, efficiencies of utilisation of incident photosynthetic photon flux density (PPFD) and rates of ribulose-1,6-bisphosphate (RuBP) regeneration. Correlated with differences in photosynthetic capacity were differences in chlorophyll contents but not differences in leaf nitrogen content. Differences in interspecific stomatal behaviour resulted in significantly different transpiration rates which in combination with differences in assimilation rates resulted in differences in water-use efficiency. The absolute amounts of water transpired, although significantly different among species, were moderate to high in comparison with species from other ecosystems and were typical of mesophytes. Transpiration rates in combination with plant hydraulic conductances and soil water availability resulted in leaf water potentials that were not very negative and none of the investigated species showed evidence of osmotic adjustment. The volume of water transpired by each of the species per unit land surface area was estimated from the relationship between abiotic factors and plant water loss. These relationships varied among species and had varying degrees of predictability as a result of differences in stomatal behaviour between the three species. The water requirements of A. populifolia and S. plumieri were adequately met by the water supplied by rainfall and the water stored in the dune sands. It was therefore not necessary to invoke the utilisation of ground water or the process of internal dew formation to supply sufficient water to meet the requirements. However, I. pes-caprae despite its lower transpiration rates and due to its higher biomass, lost greater volumes of water per unit dune surface area than either A. populifolia or S. plumieri. This resulted in periods of potential water limitation for I. pes-caprae. Incident light was the most important determinant of leaf photosynthetic CO₂ assimilation and transpiration, particularly as a linear relationship between incident PPFD and atmospheric vapour pressure deficit (VPD) could be demonstrated. Whole plant photosynthetic production by S. plumieri was shown to be light limited as a result of mutual shading despite high incident and reflected PPFD occurring in the foredune environment. The leaf hair-layer of A. populifolia was shown to be important in reducing transmitted UV and hence reducing photoinhibition but it also caused reduced transpiration rates because of the thicker boundary layer and thus increased leaf temperatures. The nutrient content of above-ground plant parts of the investigated species were typical of higher plants despite the low nutrient content measured for the dune soils. With the possible exception of nitrogen the nutrient demand created by above-ground production was adequately met by the supply of nutrients either from sand-water or from aquifer-water transpired by the plants. Differences in the volumes of water transpired, and hence the quantity of nutrients potentially taken up via the transpiration stream, resulted in interspecific differences in above-ground plant macronutrient content. The reallocation patterns of nutrients differed both between the various nutrients measured and interspecifically. Standing biomass and the density of plants per unit land area was low in comparison to that of other ecosystems and was different among investigated species. This may be important in maintaining the adequate supply of resources (water, nutrients and light). As a result of the interspecific differences in biomass when production was expressed per unit land surface area the resultant productivity was not dissimilar among species. Productivity was high when comparisons were made with species from other ecosystems. No single resource (water, nutrients or light) could be identified as the controlling factor in the foredune environment and a combination of both resource stress and environmental disturbance are likely to be involved. Physiology, production, growth and growth characteristics conveyed certain adaptive advantages to these species in respect to both resource stress and environmental disturbance. Interspecific differences in these adaptations can be used to offer explanations for the observed microhabitat preferences of the three investigated species. Furthermore features common to all three species offer some explanations as to why these species and not others are able to inhabit the foredunes.
- Full Text:
- Date Issued: 2002
- Authors: Ripley, B S
- Date: 2002
- Subjects: Sand dune plants -- South Africa -- Eastern Cape Sand dune ecology -- South Africa -- Eastern Cape Sand dune plants -- Ecophysiology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4222 , http://hdl.handle.net/10962/d1003791
- Description: Understanding the mechanisms and adaptations that allow only certain species to thrive in the potentially stressful foredune environment requires a knowledge of the basic ecophysiology of foredune species. Ecophysiological measurements were conducted on the foredune pioneer species Arctotheca populifolia (Berg.) Norl., Ipomoea pes-caprae(L.) R. Br. and Scaevola plumieri (L.) Vahl. and showed significant differences among species with respect to the physiology associated with biomass production, water and nutrient relations. Differences related to CO₂ assimilation included differences in photosynthetic and respiratory rates, susceptibility to light stress and leaf and stem non-structural carbohydrate concentrations. These resulted in differences in primary production rates of shoots. Mechanisms leading to the differences in CO₂ assimilation among species included differences in stomatal behaviour, carboxylation efficiencies, efficiencies of utilisation of incident photosynthetic photon flux density (PPFD) and rates of ribulose-1,6-bisphosphate (RuBP) regeneration. Correlated with differences in photosynthetic capacity were differences in chlorophyll contents but not differences in leaf nitrogen content. Differences in interspecific stomatal behaviour resulted in significantly different transpiration rates which in combination with differences in assimilation rates resulted in differences in water-use efficiency. The absolute amounts of water transpired, although significantly different among species, were moderate to high in comparison with species from other ecosystems and were typical of mesophytes. Transpiration rates in combination with plant hydraulic conductances and soil water availability resulted in leaf water potentials that were not very negative and none of the investigated species showed evidence of osmotic adjustment. The volume of water transpired by each of the species per unit land surface area was estimated from the relationship between abiotic factors and plant water loss. These relationships varied among species and had varying degrees of predictability as a result of differences in stomatal behaviour between the three species. The water requirements of A. populifolia and S. plumieri were adequately met by the water supplied by rainfall and the water stored in the dune sands. It was therefore not necessary to invoke the utilisation of ground water or the process of internal dew formation to supply sufficient water to meet the requirements. However, I. pes-caprae despite its lower transpiration rates and due to its higher biomass, lost greater volumes of water per unit dune surface area than either A. populifolia or S. plumieri. This resulted in periods of potential water limitation for I. pes-caprae. Incident light was the most important determinant of leaf photosynthetic CO₂ assimilation and transpiration, particularly as a linear relationship between incident PPFD and atmospheric vapour pressure deficit (VPD) could be demonstrated. Whole plant photosynthetic production by S. plumieri was shown to be light limited as a result of mutual shading despite high incident and reflected PPFD occurring in the foredune environment. The leaf hair-layer of A. populifolia was shown to be important in reducing transmitted UV and hence reducing photoinhibition but it also caused reduced transpiration rates because of the thicker boundary layer and thus increased leaf temperatures. The nutrient content of above-ground plant parts of the investigated species were typical of higher plants despite the low nutrient content measured for the dune soils. With the possible exception of nitrogen the nutrient demand created by above-ground production was adequately met by the supply of nutrients either from sand-water or from aquifer-water transpired by the plants. Differences in the volumes of water transpired, and hence the quantity of nutrients potentially taken up via the transpiration stream, resulted in interspecific differences in above-ground plant macronutrient content. The reallocation patterns of nutrients differed both between the various nutrients measured and interspecifically. Standing biomass and the density of plants per unit land area was low in comparison to that of other ecosystems and was different among investigated species. This may be important in maintaining the adequate supply of resources (water, nutrients and light). As a result of the interspecific differences in biomass when production was expressed per unit land surface area the resultant productivity was not dissimilar among species. Productivity was high when comparisons were made with species from other ecosystems. No single resource (water, nutrients or light) could be identified as the controlling factor in the foredune environment and a combination of both resource stress and environmental disturbance are likely to be involved. Physiology, production, growth and growth characteristics conveyed certain adaptive advantages to these species in respect to both resource stress and environmental disturbance. Interspecific differences in these adaptations can be used to offer explanations for the observed microhabitat preferences of the three investigated species. Furthermore features common to all three species offer some explanations as to why these species and not others are able to inhabit the foredunes.
- Full Text:
- Date Issued: 2002