Diversion Programmes and Empowerment: A Case Study of Young Offenders’ Experiences in the Buffalo City Metropolitan and Amathole District Municipalities in the Eastern Cape Province of South Africa
- Authors: Mangwiro, Vongai P
- Date: 2020
- Subjects: Social work with criminals Social work with juvenile delinquents
- Language: English
- Type: Thesis , Doctoral , PhD (Social Work)
- Identifier: http://hdl.handle.net/10353/18031 , vital:42006
- Description: Crime amongst the young in South Africa has been high since the attainment of democracy in 1994. Diversion programmes were established through the National Framework Chid Justice Act of 2008, as part of a plethora of measures to curb the ever spiralling problem of crime amongst the youth. The purpose of this thesis was to investigate the experiences of young offenders regarding their empowerment vis-à-vis diversion programmes in the Buffalo City Metropolitan and Amathole District Municipalities in the Eastern Cape Province. Underpinned by the Empowerment and Social Control Theories, the study adopted a qualitative research paradigm and used focus group discussions and in-depth interviews amongst thirty-five young offenders and five social workers, who work as probation officers at NICRO, to collect data, which was analysed using thematic analysis. The major findings indicated that diversion programmes are effective in reducing the number of children who commit crimes in these two municipalities and in influencing their behavioural change, resulting in fewer chances of re-offending. The Life Skills Programme was identified as the most effective programme, in comparison to the other programmes, such as the Community pre-trial Service Programme, in changing the behaviour of the young offenders, as it helps them to discover themselves; learn respect for the self and others in the community; help with family and community reintegration; and helps them focus on who they want to be in the future. In spite of such positive attributes for the diversion programmes, the study observed that there are challenges being faced by the implementing organisation, NICRO. These include high caseloads; lack of support from the probation officers who refer young offenders; limited support from parents; paucity of financial resources; lack of transport; poor v coordination from the courts; and delays in the implementation of some accredited but not credited programmes. Overall, the study concluded that diversion programmes in the Buffalo city Metropolitan and Amathole district municipalities in the Eastern Cape suffer due to weak partnerships between different organisations and stakeholders that are supposed to complement the efforts of the judiciary. From the research findings above, it is recommended that the Child Justice System should promote a multi-sectored approach in order to restore and reunify all the stakeholders, working with children in conflict with the law. This adds more roles and responsibilities for the various stakeholders, such as the Department of Justice and Department of Social development. Furthermore, there is a need to increase the monitoring and evaluation of diversion programmes to advance accountability and improve effectiveness; and there is a need to enhance the efficiency of accrediting authorities to timeously accredit other diversion programmes that, so far, have not yet been accredited, but may be useful in empowering young offenders. Therefore, the study proposes an extension of the framework with additions of strategies to support diversion programmes at NICRO, through a stakeholder extension to the model allocating more roles and responsibilities for stakeholders in the Child Justice system, in order for diversion programmes to effectively achieve desired goals.
- Full Text:
- Date Issued: 2020
- Authors: Mangwiro, Vongai P
- Date: 2020
- Subjects: Social work with criminals Social work with juvenile delinquents
- Language: English
- Type: Thesis , Doctoral , PhD (Social Work)
- Identifier: http://hdl.handle.net/10353/18031 , vital:42006
- Description: Crime amongst the young in South Africa has been high since the attainment of democracy in 1994. Diversion programmes were established through the National Framework Chid Justice Act of 2008, as part of a plethora of measures to curb the ever spiralling problem of crime amongst the youth. The purpose of this thesis was to investigate the experiences of young offenders regarding their empowerment vis-à-vis diversion programmes in the Buffalo City Metropolitan and Amathole District Municipalities in the Eastern Cape Province. Underpinned by the Empowerment and Social Control Theories, the study adopted a qualitative research paradigm and used focus group discussions and in-depth interviews amongst thirty-five young offenders and five social workers, who work as probation officers at NICRO, to collect data, which was analysed using thematic analysis. The major findings indicated that diversion programmes are effective in reducing the number of children who commit crimes in these two municipalities and in influencing their behavioural change, resulting in fewer chances of re-offending. The Life Skills Programme was identified as the most effective programme, in comparison to the other programmes, such as the Community pre-trial Service Programme, in changing the behaviour of the young offenders, as it helps them to discover themselves; learn respect for the self and others in the community; help with family and community reintegration; and helps them focus on who they want to be in the future. In spite of such positive attributes for the diversion programmes, the study observed that there are challenges being faced by the implementing organisation, NICRO. These include high caseloads; lack of support from the probation officers who refer young offenders; limited support from parents; paucity of financial resources; lack of transport; poor v coordination from the courts; and delays in the implementation of some accredited but not credited programmes. Overall, the study concluded that diversion programmes in the Buffalo city Metropolitan and Amathole district municipalities in the Eastern Cape suffer due to weak partnerships between different organisations and stakeholders that are supposed to complement the efforts of the judiciary. From the research findings above, it is recommended that the Child Justice System should promote a multi-sectored approach in order to restore and reunify all the stakeholders, working with children in conflict with the law. This adds more roles and responsibilities for the various stakeholders, such as the Department of Justice and Department of Social development. Furthermore, there is a need to increase the monitoring and evaluation of diversion programmes to advance accountability and improve effectiveness; and there is a need to enhance the efficiency of accrediting authorities to timeously accredit other diversion programmes that, so far, have not yet been accredited, but may be useful in empowering young offenders. Therefore, the study proposes an extension of the framework with additions of strategies to support diversion programmes at NICRO, through a stakeholder extension to the model allocating more roles and responsibilities for stakeholders in the Child Justice system, in order for diversion programmes to effectively achieve desired goals.
- Full Text:
- Date Issued: 2020
Effect of increasing fossil shell flour levels on digestive and metabolic utilization, health, body weight change and wool production, and quality in Dohne-Merino wethers
- Authors: Ikusika, Olusegun Oyebade
- Date: 2020
- Subjects: Merino sheep Sheep -- Quality
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10353/18465 , vital:42542
- Description: The study's broad objective was to assess growth performance, blood and parasitic profiles, wool parameters, methane emission, and nutritional status of Dohne-Merino wethers fed diets supplemented with varying levels of fossil shell flour. Twenty-four Dohne-Merino wethers, averagely weighing 20.0±1.50 kg, were divided into four groups and used in this study. The effects of varying inclusion levels of fossil shell flour (FSF) (0, 2, 4, and 6 %) on feed intake, water intake, nutrient digestibility, N-retention, hematobiochemical and parasitic profiles, body condition scores, feed preference, wool parameters and methane output were determined. The influence of FSF's varying inclusion levels on fermentation parameters, in vitro true digestibility, and relative feed values were also determined. Wethers fed with 4% FSF inclusion level diet showed the highest (P<0.05) values for dry matter intake, average daily weight gain, N retention, (Nitrogen retention) and apparent digestibility of crude protein (CP), Ether Extract (EE) and Ash 6 % (P < 0.05). The urinary N and fecal N were lowest in wethers fed 4% FSF inclusion level and highest in those fed on diets without FSF (P < 0.05). Water intake was highest in wethers fed 0% FSF diet, followed by those fed on 4% and lowest in 6% FSF (P< 0.05). There was a significant increase in white blood cell counts in wethers fed on a diet with 4% and 6% FSF inclusion levels from day 10 to 100 compared to wethers fed on a diet with 0% and 2% FSF (P <0.05). Red blood cell counts also increased significantly in wethers fed on a diet containing 4% FSF, but a slight increase in wethers with 6 % FSF diet, throughout the experimental period (P < 0.05). Blood urea was highest in wethers fed 0% FSF inclusion level and lowest in 6% at day 30 to day 100. Wethers on 4% FSF diet showed an increase in blood urea from day 30 to day 100 (P < 0.05) while wethers on 0% and 2% remained unchanged (P<0.05) during this period and not different (P > 0.05) from wethers on 4% FSF as well. The total protein concentration, albumin, total bilirubin, Na, K, glucose, cholesterol, and liver enzymes were normal for wethers. However, serum creatinine level was lower in wethers fed on 4% FSF than those on 0% FSF (P < 0.01). Haemonchus and Coccidian fecal egg counts were low in wethers fed diets with 2%, 4%, and 6 % FSF (P < 0.01) compared 11 with wethers fed with 0% FSF inclusion level during the same period. The body condition score of wethers fed on diets with 2%, 4%, and 6% FSF inclusion levels were higher than those on 0% (P < 0.05). Wool yield, staple length, the coefficient variation of the fibre diameter, and fibre of wethers fed on diets with FSF were higher than those without FSF (P < 0.05). The fibre diameter of the wethers fed on FSF supplemented diets was the same as those on 0 % FSF (P > 0.05). The wethers spent more time on FSF supplemented diets and consumed more feed compared to that without FSF supplemented (P < 0.05). The levels of FSF inclusion in the diet affected the enteric methane output (ppm-m), where 4 % FSF had the highest enteric methane output while wethers on 2 % FSF had the lowest methane output (P < 0.05). Resting wethers produced more methane (g/day) than those feeding or standing (P < 0.05). Increasing levels of FSF did not affect ruminal temperature and pH. Ammonia-N increased with increasing FSF except in wethers fed on a diet with 4% FSF (P < 0.01). The total molar concentrations of the wethers' volatile fatty acids decreased with increasing FSF levels (P > 0.05). The acetic propionic ratio of the wethers also decreased except at a 4% inclusion level. The in vitro true digestibility dry matter (IVTDDM), in vitro true digestibility neutral detergent fibre (IVTDNDF), and in vitro true digestibility acid detergent fibre (IVTDADF) of the wethers decreased up to 4% FSF inclusion but tended to increase at 6% inclusion. This study's result as one of the pioneer studies in Dohne-Marino wethers showed that FSF treatment has the potential to improve the nutritional status of the animal and the animal performance and wool quality. Health-wise, FSF decrease nematode population and boost animal immunity as seen in RBC and WBC counts. It also can play a major role in protecting the environment, as seen in its reduction in feacal and urinary nitrogen, which is heavily involved in environmental pollution. Result also confirmed that the best period to target for methane mitigation in ruminants is the resting period. In conclusion, the inclusion of FSF in the diet of Dohne-Merino wethers has the potential to improve the overall performance, with a 4% FSF inclusion level having optimal productivity. However, future research is required to investigate FSF's effect on meat quality, rumen microbial community, in-vivo digestibility, and milk production.
- Full Text:
- Date Issued: 2020
- Authors: Ikusika, Olusegun Oyebade
- Date: 2020
- Subjects: Merino sheep Sheep -- Quality
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10353/18465 , vital:42542
- Description: The study's broad objective was to assess growth performance, blood and parasitic profiles, wool parameters, methane emission, and nutritional status of Dohne-Merino wethers fed diets supplemented with varying levels of fossil shell flour. Twenty-four Dohne-Merino wethers, averagely weighing 20.0±1.50 kg, were divided into four groups and used in this study. The effects of varying inclusion levels of fossil shell flour (FSF) (0, 2, 4, and 6 %) on feed intake, water intake, nutrient digestibility, N-retention, hematobiochemical and parasitic profiles, body condition scores, feed preference, wool parameters and methane output were determined. The influence of FSF's varying inclusion levels on fermentation parameters, in vitro true digestibility, and relative feed values were also determined. Wethers fed with 4% FSF inclusion level diet showed the highest (P<0.05) values for dry matter intake, average daily weight gain, N retention, (Nitrogen retention) and apparent digestibility of crude protein (CP), Ether Extract (EE) and Ash 6 % (P < 0.05). The urinary N and fecal N were lowest in wethers fed 4% FSF inclusion level and highest in those fed on diets without FSF (P < 0.05). Water intake was highest in wethers fed 0% FSF diet, followed by those fed on 4% and lowest in 6% FSF (P< 0.05). There was a significant increase in white blood cell counts in wethers fed on a diet with 4% and 6% FSF inclusion levels from day 10 to 100 compared to wethers fed on a diet with 0% and 2% FSF (P <0.05). Red blood cell counts also increased significantly in wethers fed on a diet containing 4% FSF, but a slight increase in wethers with 6 % FSF diet, throughout the experimental period (P < 0.05). Blood urea was highest in wethers fed 0% FSF inclusion level and lowest in 6% at day 30 to day 100. Wethers on 4% FSF diet showed an increase in blood urea from day 30 to day 100 (P < 0.05) while wethers on 0% and 2% remained unchanged (P<0.05) during this period and not different (P > 0.05) from wethers on 4% FSF as well. The total protein concentration, albumin, total bilirubin, Na, K, glucose, cholesterol, and liver enzymes were normal for wethers. However, serum creatinine level was lower in wethers fed on 4% FSF than those on 0% FSF (P < 0.01). Haemonchus and Coccidian fecal egg counts were low in wethers fed diets with 2%, 4%, and 6 % FSF (P < 0.01) compared 11 with wethers fed with 0% FSF inclusion level during the same period. The body condition score of wethers fed on diets with 2%, 4%, and 6% FSF inclusion levels were higher than those on 0% (P < 0.05). Wool yield, staple length, the coefficient variation of the fibre diameter, and fibre of wethers fed on diets with FSF were higher than those without FSF (P < 0.05). The fibre diameter of the wethers fed on FSF supplemented diets was the same as those on 0 % FSF (P > 0.05). The wethers spent more time on FSF supplemented diets and consumed more feed compared to that without FSF supplemented (P < 0.05). The levels of FSF inclusion in the diet affected the enteric methane output (ppm-m), where 4 % FSF had the highest enteric methane output while wethers on 2 % FSF had the lowest methane output (P < 0.05). Resting wethers produced more methane (g/day) than those feeding or standing (P < 0.05). Increasing levels of FSF did not affect ruminal temperature and pH. Ammonia-N increased with increasing FSF except in wethers fed on a diet with 4% FSF (P < 0.01). The total molar concentrations of the wethers' volatile fatty acids decreased with increasing FSF levels (P > 0.05). The acetic propionic ratio of the wethers also decreased except at a 4% inclusion level. The in vitro true digestibility dry matter (IVTDDM), in vitro true digestibility neutral detergent fibre (IVTDNDF), and in vitro true digestibility acid detergent fibre (IVTDADF) of the wethers decreased up to 4% FSF inclusion but tended to increase at 6% inclusion. This study's result as one of the pioneer studies in Dohne-Marino wethers showed that FSF treatment has the potential to improve the nutritional status of the animal and the animal performance and wool quality. Health-wise, FSF decrease nematode population and boost animal immunity as seen in RBC and WBC counts. It also can play a major role in protecting the environment, as seen in its reduction in feacal and urinary nitrogen, which is heavily involved in environmental pollution. Result also confirmed that the best period to target for methane mitigation in ruminants is the resting period. In conclusion, the inclusion of FSF in the diet of Dohne-Merino wethers has the potential to improve the overall performance, with a 4% FSF inclusion level having optimal productivity. However, future research is required to investigate FSF's effect on meat quality, rumen microbial community, in-vivo digestibility, and milk production.
- Full Text:
- Date Issued: 2020
Study habits and learning styles as correlates of grade 11 students’ academic performance in mathematical literacy in the Amathole Education District
- Authors: Yako, Mzwandile John-Mott
- Date: 2019
- Subjects: Academic performance
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/16687 , vital:40743
- Description: This study investigated whether there was correlation in study habits and learning styles with Mathematical Literacy among the Grade 11 (eleven) high school learners. The Amatole Education District was chosen for this study since it is composed of urban and rural schools. Since Mathematical Literacy was introduced in the system of education in South Africa with the understanding that learners who are finding it a challenge to study Mathematics be complemented with Mathematical Literacy to provide them with skills that are a prerequisite for tertiary level and participation in the economic development. The study purposed to establish whether there was a relationship between academic performance with study habits and learning styles in Mathematical Literacy. The study used the post-positivistic paradigm; the approach was quantitative and the design was descriptive correlational. In sampling probability, cluster sampling was used based on the number of high schools in the Amatole Education District of the Eastern Cape. It was then followed by sub-sampling of learners in Grade 11 (eleven) whose mathematical Literacy skills and performance were being investigated in this study. The theory of Covey on study habits and Kolb’s theory on learning styles were used as a theoretical framework for the study. The data collection instrument used was a closed-ended questionnaire based on a Likert scale measurement. Confidentiality and anonymity were emphasized with informed consent in place. Data was analyzed using SPSS software and Microsoft Excel. The results showed a significant relationship between note taking, writing skills and Mathematical Literacy skills and performance. The findings on the learning styles indicated no significant relationship between socio-demographic factors (visual language, visual numerical, auditory-numerical e.tc.) and academic performance in Mathematical Literacy. This research revealed that study habits had an impact on the academic performance of learners in mathematical literacy. This relationship between academic performance and study habits is an indication that learners needed to improve in their use of English as a second language, especially on note taking, writing skills and Mathematical Literacy.
- Full Text:
- Date Issued: 2019
- Authors: Yako, Mzwandile John-Mott
- Date: 2019
- Subjects: Academic performance
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10353/16687 , vital:40743
- Description: This study investigated whether there was correlation in study habits and learning styles with Mathematical Literacy among the Grade 11 (eleven) high school learners. The Amatole Education District was chosen for this study since it is composed of urban and rural schools. Since Mathematical Literacy was introduced in the system of education in South Africa with the understanding that learners who are finding it a challenge to study Mathematics be complemented with Mathematical Literacy to provide them with skills that are a prerequisite for tertiary level and participation in the economic development. The study purposed to establish whether there was a relationship between academic performance with study habits and learning styles in Mathematical Literacy. The study used the post-positivistic paradigm; the approach was quantitative and the design was descriptive correlational. In sampling probability, cluster sampling was used based on the number of high schools in the Amatole Education District of the Eastern Cape. It was then followed by sub-sampling of learners in Grade 11 (eleven) whose mathematical Literacy skills and performance were being investigated in this study. The theory of Covey on study habits and Kolb’s theory on learning styles were used as a theoretical framework for the study. The data collection instrument used was a closed-ended questionnaire based on a Likert scale measurement. Confidentiality and anonymity were emphasized with informed consent in place. Data was analyzed using SPSS software and Microsoft Excel. The results showed a significant relationship between note taking, writing skills and Mathematical Literacy skills and performance. The findings on the learning styles indicated no significant relationship between socio-demographic factors (visual language, visual numerical, auditory-numerical e.tc.) and academic performance in Mathematical Literacy. This research revealed that study habits had an impact on the academic performance of learners in mathematical literacy. This relationship between academic performance and study habits is an indication that learners needed to improve in their use of English as a second language, especially on note taking, writing skills and Mathematical Literacy.
- Full Text:
- Date Issued: 2019
Bayliss-Hillman adducts as scaffolds for the construction of novel compounds with medicinal potential
- Authors: Idahosa, Kenudi Christiana
- Date: 2012
- Subjects: Antimalarials -- Research Malaria -- Chemotherapy -- Research AIDS (Disease) -- Treatment -- Research AIDS (Disease) -- Chemotherapy -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4410 , http://hdl.handle.net/10962/d1006763
- Description: This project has focused on exploring the application of Baylis-Hillman (BH) {a.k.a. Morita-Baylis-Hillman (MBH)} scaffolds in the construction of various compounds with medicinal potential. A series of 2-nitrobenzaldehydes has been treated under BH conditions, with two different activated alkenes, viz., (MVK) and methyl acrylate, using (DABCO) or (3-HQ) as catalyst. While most of the BH reactions were carried out at room temperature, some reactions were conducted using microwave irradiation. The resulting BH adducts have been subjected to dehydration, conjugate addition and allylic substitution to obtain appropriate intermediates, which have been used in turn, to synthesize possible lead compounds, viz., cinnamate esters as HIV-1 integrase inhibitors, 3-(aminomethyl)quinolines and quinolones as anti-malarials and cinnamate ester-AZT conjugates as dual-action HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. Conjugate addition reactions of methyl acrylate-derived BH β-hydroxy esters with the amines, piperidine, propargylamine and 2-amino-5-(diethylamino)pentane, has afforded a range of products as diastereomeric mixtures in moderate to excellent yields. Catalytic hydrogenation of the aminomethy β-hydroxy esters derivatives, using a palladium-oncarbon (Pd-C) catalyst, has afforded the corresponding, novel 3-aminomethyl-2- quinolone derivatives in moderate yields. Effective allylic substitution reactions of the MVK-derived BH β-hydroxy ketones (via a conjugate addition-elimination pathway) using in situ-generated HCl has afforded the corresponding α-chloromethyl derivatives, which have been reacted with various amines, including piperidine, piperazine, propargylamine and 2-amino-5-(diethylamino)pentane, to yield α-aminomethyl derivatives. Catalytic hydrogenation of selected α-aminomethyl derivatives, using a Pd-C catalyst, has afforded the corresponding, novel 3- (aminomethyl)-2-methylquinoline derivatives in low to moderate yields. A bioassay, conducted on a 6-hydroxy-2-methyl-3-[(piperidin-1-yl)methyl]quinoline isolated early in the study indicated anti-malarial activity and prompted further efforts in the synthesis of analogous compounds. Reaction of the methyl acrylate-derived BH adducts with POCl3 has provided access to α-(chloromethyl)cinnamate ester derivatives, which have been aminated to afford α- (aminomethyl)cinnamate ester derivatives as potential HIV-1 integrase inhibitors. The α- (propargylaminomethyl)cinnamates were used, in turn, as substrates for the “click chemistry” reaction with 3'-azido-3'-deoxythymidine (AZT– an azide and an established reverse transcriptase HIV-1 inhibitor) to afford cinnamate ester-AZT conjugates as potential dual-action HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. Computer modelling and docking studies of a cinnamate ester-AZT conjugate into the HIV-1 integrase and reverse transcriptase active-sites revealed potential hydrogen-bonding interactions with amino acid residues within the receptor cavities. The isolated products have been appropriately characterized using IR, 1- and 2-D NMR and HRMS techniques, while elucidation of the stereochemistry of the double bond in the BH-derived halomethyl derivatives has been assigned on the basis of NOE, computer modelling and X-ray crystallographic data.
- Full Text:
- Date Issued: 2012
- Authors: Idahosa, Kenudi Christiana
- Date: 2012
- Subjects: Antimalarials -- Research Malaria -- Chemotherapy -- Research AIDS (Disease) -- Treatment -- Research AIDS (Disease) -- Chemotherapy -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4410 , http://hdl.handle.net/10962/d1006763
- Description: This project has focused on exploring the application of Baylis-Hillman (BH) {a.k.a. Morita-Baylis-Hillman (MBH)} scaffolds in the construction of various compounds with medicinal potential. A series of 2-nitrobenzaldehydes has been treated under BH conditions, with two different activated alkenes, viz., (MVK) and methyl acrylate, using (DABCO) or (3-HQ) as catalyst. While most of the BH reactions were carried out at room temperature, some reactions were conducted using microwave irradiation. The resulting BH adducts have been subjected to dehydration, conjugate addition and allylic substitution to obtain appropriate intermediates, which have been used in turn, to synthesize possible lead compounds, viz., cinnamate esters as HIV-1 integrase inhibitors, 3-(aminomethyl)quinolines and quinolones as anti-malarials and cinnamate ester-AZT conjugates as dual-action HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. Conjugate addition reactions of methyl acrylate-derived BH β-hydroxy esters with the amines, piperidine, propargylamine and 2-amino-5-(diethylamino)pentane, has afforded a range of products as diastereomeric mixtures in moderate to excellent yields. Catalytic hydrogenation of the aminomethy β-hydroxy esters derivatives, using a palladium-oncarbon (Pd-C) catalyst, has afforded the corresponding, novel 3-aminomethyl-2- quinolone derivatives in moderate yields. Effective allylic substitution reactions of the MVK-derived BH β-hydroxy ketones (via a conjugate addition-elimination pathway) using in situ-generated HCl has afforded the corresponding α-chloromethyl derivatives, which have been reacted with various amines, including piperidine, piperazine, propargylamine and 2-amino-5-(diethylamino)pentane, to yield α-aminomethyl derivatives. Catalytic hydrogenation of selected α-aminomethyl derivatives, using a Pd-C catalyst, has afforded the corresponding, novel 3- (aminomethyl)-2-methylquinoline derivatives in low to moderate yields. A bioassay, conducted on a 6-hydroxy-2-methyl-3-[(piperidin-1-yl)methyl]quinoline isolated early in the study indicated anti-malarial activity and prompted further efforts in the synthesis of analogous compounds. Reaction of the methyl acrylate-derived BH adducts with POCl3 has provided access to α-(chloromethyl)cinnamate ester derivatives, which have been aminated to afford α- (aminomethyl)cinnamate ester derivatives as potential HIV-1 integrase inhibitors. The α- (propargylaminomethyl)cinnamates were used, in turn, as substrates for the “click chemistry” reaction with 3'-azido-3'-deoxythymidine (AZT– an azide and an established reverse transcriptase HIV-1 inhibitor) to afford cinnamate ester-AZT conjugates as potential dual-action HIV-1 integrase-reverse transcriptase (IN-RT) inhibitors. Computer modelling and docking studies of a cinnamate ester-AZT conjugate into the HIV-1 integrase and reverse transcriptase active-sites revealed potential hydrogen-bonding interactions with amino acid residues within the receptor cavities. The isolated products have been appropriately characterized using IR, 1- and 2-D NMR and HRMS techniques, while elucidation of the stereochemistry of the double bond in the BH-derived halomethyl derivatives has been assigned on the basis of NOE, computer modelling and X-ray crystallographic data.
- Full Text:
- Date Issued: 2012
Electrochemistry and photophysicochemical studies of titanium, tantalum and vanadium phthalocyanines in the presence of nanomaterials
- Authors: Chauke, Vongani Portia
- Date: 2012
- Subjects: Phthalocyanines -- Synthesis Electrochemistry Titanium Tantalum Vanadium
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4313 , http://hdl.handle.net/10962/d1004971
- Description: The syntheses of tetra- and octa-substituted phthalocyanine complexes of titanium (IV) oxide vanadium (IV) oxide and tantalum (V) hydroxide and their electrochemical characterisation are presented in this work. The structures and purity of these complexes were confirmed by NMR, infrared and mass spectroscopies and elemental analysis. They show good solubility in most common solvents especially non-viscous solvents such as dichloromethane and chloroform. The cyclic voltammograms (CV) showed reversible to quasi reversible behavior for all the reduction couples and the oxidation peaks were irreversible. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes. The synthesis of gold nanoparticles and their conjugation with the new phthalocyanines was carried out. Similarly, single walled carbon nanotubes were conjugated to selected tantalum complexes and the characterization of all the nanomaterials and their conjugates using different techniques that include TEM, XRD and AFM is also presented in this work. The photophysical and photochemical properties and photocatalytic oxidation of cyclohexene properties of the newly synthesised in the presence of gold nanoparticles were investigated. The compounds were stable, well within the stability range for phthalocyanines. The singlet oxygen quantum yield values increased drastically in the presence of gold nanoparticles. The photocatalytic products obtained from the reaction were cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,4-cyclohexanediol. The percentage conversion values, yields and selectivity values improved significantly in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The electrocatalytic oxidation of bisphenol A and p-nitrophenol was carried out using nickel tetraamino phthalocyanine and all the newly synthesised metallophthalocyanine in the presence of gold nanoparticles and single walled carbon nanotubes. The charge transfer behaviour of AuNPs was enhanced in the presence of TaPc, TiPc and VPc complexes. The presence of single walled carbon nanotubes further improved electron transfer and minimised electrode passivation.
- Full Text:
- Date Issued: 2012
- Authors: Chauke, Vongani Portia
- Date: 2012
- Subjects: Phthalocyanines -- Synthesis Electrochemistry Titanium Tantalum Vanadium
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4313 , http://hdl.handle.net/10962/d1004971
- Description: The syntheses of tetra- and octa-substituted phthalocyanine complexes of titanium (IV) oxide vanadium (IV) oxide and tantalum (V) hydroxide and their electrochemical characterisation are presented in this work. The structures and purity of these complexes were confirmed by NMR, infrared and mass spectroscopies and elemental analysis. They show good solubility in most common solvents especially non-viscous solvents such as dichloromethane and chloroform. The cyclic voltammograms (CV) showed reversible to quasi reversible behavior for all the reduction couples and the oxidation peaks were irreversible. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes. The synthesis of gold nanoparticles and their conjugation with the new phthalocyanines was carried out. Similarly, single walled carbon nanotubes were conjugated to selected tantalum complexes and the characterization of all the nanomaterials and their conjugates using different techniques that include TEM, XRD and AFM is also presented in this work. The photophysical and photochemical properties and photocatalytic oxidation of cyclohexene properties of the newly synthesised in the presence of gold nanoparticles were investigated. The compounds were stable, well within the stability range for phthalocyanines. The singlet oxygen quantum yield values increased drastically in the presence of gold nanoparticles. The photocatalytic products obtained from the reaction were cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,4-cyclohexanediol. The percentage conversion values, yields and selectivity values improved significantly in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The electrocatalytic oxidation of bisphenol A and p-nitrophenol was carried out using nickel tetraamino phthalocyanine and all the newly synthesised metallophthalocyanine in the presence of gold nanoparticles and single walled carbon nanotubes. The charge transfer behaviour of AuNPs was enhanced in the presence of TaPc, TiPc and VPc complexes. The presence of single walled carbon nanotubes further improved electron transfer and minimised electrode passivation.
- Full Text:
- Date Issued: 2012
Metallophthalocyanine derivatives as catalysts for the detection of sulphur dioxide, cyanide, nitrite and amino acids
- Authors: Thamae, Mamothibe Amelia
- Date: 2003
- Subjects: Cyanides Nitric oxide Electrochemistry Nitrites Suplhur dioxide Amino acids
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4295 , http://hdl.handle.net/10962/d1004542
- Description: Electrocatalytic reduction and oxidation of nitrite using cobalt phthalocyanine derivatives was studied. The detection limit of 1 x 10⁻¹° mol dm⁻³ was achieved when these molecules were employed as catalysts for nitrite detection. The mechanisms for nitrite catalysis were proposed. The position of the peripheral substituents on cobalt porphyrazines (related to cobalt phthalocyanines) affected the catalytic activity of these complexes. The highest activity for nitrite reduction was observed on the cobalt(II) 2,3-tetramethyltetrapyridinoporphyrazine ([CoTm-2,3-tppa]⁴⁺), with cobalt phthalocyanine showing the lowest activity, and the cobalt(II) 3,4- tetramethyltetrapyridinoporphyrazine ([CoTm-3,4-tppa]⁴⁺), showing intermediate behaviour. A mixture of a negatively charged cobalt(II) tetrasulfophthalocyanine ([Co¹¹TSPc]⁴⁻) and a positively charged [CoTm-3,4-tppa]⁴⁺ showed better activity for nitrite reduction than did the individual components. Cobalt porphyrazines lowered the potentials for nitrite reduction in that peaking was observed, as opposed to cobalt phthalocyanine, where only the increase in currents was observed without peaking. Using the cobalt phthalocyanine derivatives, nitrite can be reduced to ammonia with high current efficiency. A glassy carbon electrode modified with [Co¹¹TSPc]⁴⁻ was employed for the determination of nitrite. Nitrate had an insignificant effect on nitrite oxidation on these modified electrodes. Electrocatalytic determination of S0₂ was studied as a function of pH at a glassy carbon electrode modified with iron(II) tetrasulfophthalocaynine. It was found that depending on pH, S0₂.xH₂0, HS0₃⁻ and/or SO₃²⁻ are the main compounds in solution and that these compounds behave differently at the electrode surface. Detection limits ranging from 4.0 ± 0.1 x 10⁻⁵ to 7.5 ± 0.1 x 10⁻⁵ mol dm⁻³ depending on pH were observed. Similar results were obtained when cobalt(II) tetrasulfophthalocaynine was employed for S0₂ catalysis under the same experimental conditions. Cysteine and histidine determination using oxidation currents was performed on glassy carbon electrodes modified with [CoTm-3,4-tppa]⁴⁺ (represented as [CoTm-3,4-tppa]⁴⁺-GCE) in pH 7 Tris buffer. The detection limit of 1.0 x 10⁻⁵ mol dm⁻³ for cysteine and 2.24 x 10⁻⁷ mol dm⁻³ for histidine were obtained. Cyanide can be detected down to 1 x 10⁻¹¹ mol dm⁻³ using [CoTm-3,4-tppa]⁴⁺-GCE in pH 10.8 buffer. Cyanide and S0₂ coordinate to the [CoTSPc]⁴⁻ species. The coordination is accompanied by oxidation of the central Co(II) metal, forming a [Co¹¹¹CoTSPc]³⁻ species. The rate constants for cyanide coordination to the [Co¹¹TSPc]⁴⁻ complex are larger than those reported for the coordination of cyanide to FePc and RuPc complexes in non-aqueous media. Autoreduction of [Co¹¹Tmtppa]⁴⁺ occurred in the presence of either histidine or cysteine, with the formation of metal reduced species, [Co¹Tmtppa(-2)]³⁺. Nitric oxide and nitrite coordinate to the [Co¹¹Tmtppa]⁴⁺ species, without auto-reduction of this species, which was observed for cysteine or histidine. The use of [Co¹¹TSPc]⁴ resulted in improved rate of interaction with nitrite when compared to the [Co¹¹Tmtppa]⁴⁺ species.
- Full Text:
- Date Issued: 2003
- Authors: Thamae, Mamothibe Amelia
- Date: 2003
- Subjects: Cyanides Nitric oxide Electrochemistry Nitrites Suplhur dioxide Amino acids
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4295 , http://hdl.handle.net/10962/d1004542
- Description: Electrocatalytic reduction and oxidation of nitrite using cobalt phthalocyanine derivatives was studied. The detection limit of 1 x 10⁻¹° mol dm⁻³ was achieved when these molecules were employed as catalysts for nitrite detection. The mechanisms for nitrite catalysis were proposed. The position of the peripheral substituents on cobalt porphyrazines (related to cobalt phthalocyanines) affected the catalytic activity of these complexes. The highest activity for nitrite reduction was observed on the cobalt(II) 2,3-tetramethyltetrapyridinoporphyrazine ([CoTm-2,3-tppa]⁴⁺), with cobalt phthalocyanine showing the lowest activity, and the cobalt(II) 3,4- tetramethyltetrapyridinoporphyrazine ([CoTm-3,4-tppa]⁴⁺), showing intermediate behaviour. A mixture of a negatively charged cobalt(II) tetrasulfophthalocyanine ([Co¹¹TSPc]⁴⁻) and a positively charged [CoTm-3,4-tppa]⁴⁺ showed better activity for nitrite reduction than did the individual components. Cobalt porphyrazines lowered the potentials for nitrite reduction in that peaking was observed, as opposed to cobalt phthalocyanine, where only the increase in currents was observed without peaking. Using the cobalt phthalocyanine derivatives, nitrite can be reduced to ammonia with high current efficiency. A glassy carbon electrode modified with [Co¹¹TSPc]⁴⁻ was employed for the determination of nitrite. Nitrate had an insignificant effect on nitrite oxidation on these modified electrodes. Electrocatalytic determination of S0₂ was studied as a function of pH at a glassy carbon electrode modified with iron(II) tetrasulfophthalocaynine. It was found that depending on pH, S0₂.xH₂0, HS0₃⁻ and/or SO₃²⁻ are the main compounds in solution and that these compounds behave differently at the electrode surface. Detection limits ranging from 4.0 ± 0.1 x 10⁻⁵ to 7.5 ± 0.1 x 10⁻⁵ mol dm⁻³ depending on pH were observed. Similar results were obtained when cobalt(II) tetrasulfophthalocaynine was employed for S0₂ catalysis under the same experimental conditions. Cysteine and histidine determination using oxidation currents was performed on glassy carbon electrodes modified with [CoTm-3,4-tppa]⁴⁺ (represented as [CoTm-3,4-tppa]⁴⁺-GCE) in pH 7 Tris buffer. The detection limit of 1.0 x 10⁻⁵ mol dm⁻³ for cysteine and 2.24 x 10⁻⁷ mol dm⁻³ for histidine were obtained. Cyanide can be detected down to 1 x 10⁻¹¹ mol dm⁻³ using [CoTm-3,4-tppa]⁴⁺-GCE in pH 10.8 buffer. Cyanide and S0₂ coordinate to the [CoTSPc]⁴⁻ species. The coordination is accompanied by oxidation of the central Co(II) metal, forming a [Co¹¹¹CoTSPc]³⁻ species. The rate constants for cyanide coordination to the [Co¹¹TSPc]⁴⁻ complex are larger than those reported for the coordination of cyanide to FePc and RuPc complexes in non-aqueous media. Autoreduction of [Co¹¹Tmtppa]⁴⁺ occurred in the presence of either histidine or cysteine, with the formation of metal reduced species, [Co¹Tmtppa(-2)]³⁺. Nitric oxide and nitrite coordinate to the [Co¹¹Tmtppa]⁴⁺ species, without auto-reduction of this species, which was observed for cysteine or histidine. The use of [Co¹¹TSPc]⁴ resulted in improved rate of interaction with nitrite when compared to the [Co¹¹Tmtppa]⁴⁺ species.
- Full Text:
- Date Issued: 2003
Interrupt-generating active data objects
- Authors: Clayton, Peter Graham
- Date: 1990
- Subjects: Parallel programming (Computer science) Electronic data processing -- Distributed processing
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4677 , http://hdl.handle.net/10962/d1006700
- Description: An investigation is presented into an interrupt-generating object model which is designed to reduce the effort of programming distributed memory multicomputer networks. The object model is aimed at the natural modelling of problem domains in which a number of concurrent entities interrupt one another as they lay claim to shared resources. The proposed computational model provides for the safe encapsulation of shared data, and incorporates inherent arbitration for simultaneous access to the data. It supplies a predicate triggering mechanism for use in conditional synchronization and as an alternative mechanism to polling. Linguistic support for the proposal requires a novel form of control structure which is able to interface sensibly with interrupt-generating active data objects. The thesis presents the proposal as an elemental language structure, with axiomatic guarantees which enforce safety properties and aid in program proving. The established theory of CSP is used to reason about the object model and its interface. An overview is presented of a programming language called HUL, whose semantics reflect the proposed computational model. Using the syntax of HUL, the application of the interrupt-generating active data object is illustrated. A range of standard concurrent problems is presented to demonstrate the properties of the interrupt-generating computational model. Furthermore, the thesis discusses implementation considerations which enable the model to be mapped precisely onto multicomputer networks, and which sustain the abstract programming level provided by the interrupt-generating active data object in the wider programming structures of HUL.
- Full Text:
- Date Issued: 1990
- Authors: Clayton, Peter Graham
- Date: 1990
- Subjects: Parallel programming (Computer science) Electronic data processing -- Distributed processing
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4677 , http://hdl.handle.net/10962/d1006700
- Description: An investigation is presented into an interrupt-generating object model which is designed to reduce the effort of programming distributed memory multicomputer networks. The object model is aimed at the natural modelling of problem domains in which a number of concurrent entities interrupt one another as they lay claim to shared resources. The proposed computational model provides for the safe encapsulation of shared data, and incorporates inherent arbitration for simultaneous access to the data. It supplies a predicate triggering mechanism for use in conditional synchronization and as an alternative mechanism to polling. Linguistic support for the proposal requires a novel form of control structure which is able to interface sensibly with interrupt-generating active data objects. The thesis presents the proposal as an elemental language structure, with axiomatic guarantees which enforce safety properties and aid in program proving. The established theory of CSP is used to reason about the object model and its interface. An overview is presented of a programming language called HUL, whose semantics reflect the proposed computational model. Using the syntax of HUL, the application of the interrupt-generating active data object is illustrated. A range of standard concurrent problems is presented to demonstrate the properties of the interrupt-generating computational model. Furthermore, the thesis discusses implementation considerations which enable the model to be mapped precisely onto multicomputer networks, and which sustain the abstract programming level provided by the interrupt-generating active data object in the wider programming structures of HUL.
- Full Text:
- Date Issued: 1990
The growth of flue-cured tobacco in acid soils
- Authors: Ryding, William Wallace
- Date: 1969
- Subjects: Flue-cured tobacco -- Zimbabwe , Acid soils -- Zimbabwe
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4495 , http://hdl.handle.net/10962/d1013110
- Description: The main effects of lime, aluminium, iron and manganese were studied in field and greenhouse grown tobacco; relations between soil and plant measurements were examined. Ground limestone, ground mixed lime, ground dolomite and slaked lime at rates equivalent to 1,000 and 2,000 lb. CaC0₃/acre increased yield and quality of flue-cured tobacco both on Triassic and granite sands, whether applied early (February/March) or late (September); the highest rate and late application were often best. Yields increased with 4,000 and 6,000 lb. dolomite/acre applied late, but quality decreased when the pH was about 6.0. Lime did not affect leaf maturity as reflected by nitrogen and reducing sugars concentration . Where leaf discolouration (slate) occurred, the best quality and least discoloured leaf had the lowest manganese concentration and was grown on limed soil. On a very acid and probably nitrogen deficient soil, lime, borax and nitrogen (nitrate only tested) reduced the discolouration and improved the quality, but potassium sulphate increased discolouration and decreased quality. Calcium concentration in the leaf was increased by lime, particularly calcitic materials, and magnesium concentration was increased by dolomite. Lime also increased the filling value and petroleum ether extract, but decreased manganese, boron, chloride and sometimes potassium, and had no effect on phosphorus, nitrogen, aluminium, iron, crude fibre, nicotine, reducing sugars and equilibrium moisture. The inorganic composition of greenhouse plants was similar; generally gypsum increased calcium concentration more than calcium carbonate but it did not affect manganese concentration, which was decreased by calcium carbonate. In the stem and roots of field grown plants (dolomite only tested), the concentration of magnesium was increased but the concentrations of calcium, potassium, aluminium and iron were unaffected. Although the concentration of nitrogen was increased and that of phosphorus was decreased in the stem, these were unaffected in the roots. Aluminium and iron behaved differently to other nutrient ions, being more concentrated in the roots than aerial plant parts. Boron and magnesium deficiencies were observed in a dry and wet year, respectively, suggesting that variable mineral deficiencies can affect responses to lime. Initially soil pH was affected more by source of lime, but later mostly by rates. Slaked lime increased the soil pH more than did ground limestone, mixed lime or dolomite. In a glasshouse experiment, pH was more important than calcium supply and in the field, the largest yields were often associated with the highest pH. In pot experiments, aluminium drastically reduced yields in nutrient solution but not in soils, whereas iron was more severe in soils; manganese had little effect on yield. Manganese was readily taken up and translocated to the tops, but aluminium and iron were mainly concentrated in the roots, as was found in field grown plants. Iron decreased manganese concentration in all plant parts and aluminium decreased calcium and manganese in nutrient solution only. Although aluminium and iron generally increased the concentration of phosphorus in the roots, they did not interfere with phosphorus transport in the plant. Manganese caused the leaf to become chlorotic and when no iron was present the upper leaves became yellow, and developed brown and white lesions. However, in soil grown plants, sufficient iron was present in the soil solution to prevent break down of tissue. Yellowing of the upper leaves also occurred when plants were grown in nutrient solution with aluminium and no iron; when both were present, the plants were darker in colour. Although aluminium damaged roots in nutrient solution, high rates of iron severely damaged leaves of plants grown in soil. Since the concentrations of aluminium, iron and manganese were decreased in the soil solution by liming, they were compared with plant growth and composition in 17 different soils, with and without lime. As was expected, lime increased soil pH. It also increased exchangeable calcium, but decreased exchangeable aluminium, iron and manganese; exchangeable magnesium and potassium and resin extractable phosphorus were not affected. As the Ratio Law does not hold for all Rhodesian soils, anion adsorption will be avoided if the soils are equilibrated with O.OOOSM CaC1₂; the concentrations of the cations in solution were affected in the same way as exchangeable cations, but phosphorus was increased. There was no relationship between yield of tobacco and its chemical composition. The correlations between soil solution data and plant composition were poor, except for manganese and phosphorus; the relation between Mn ppm. in plant vsa (superscript)Mn/a (superscript)Ca + Mg (enclosed in square root sign √) in solution, and P% vs pH₂ P0₄ or pH₂ P0₄ +½ pCa, were both curvilinear. On the other hand, all measurements of exchangeable cations were poorly correlated with plant composition. Finally yield was poorly correlated with soil solution data, and pH was as satisfactory as any other measurement tested. Manganese toxicity was observed on three soils, and a probable manganese deficiency on one. It was not possible to define a limit above which manganese toxicity occurred, but manganese deficiency developed at about 63 ppm. manganese. Variations in pH and the availability of aluminium, iron and manganese occurred when soils were incubated at about field capacity, generally the main effects having developed within seven days. In all soils, there was an initial increase in soil pH and a maximum value was reached in one to four days, decreasing by variable amounts with longer periods of incubation. Although the concentration of aluminium was larger than that of iron, the relation between both ions and soil pH was curvilinear, their concentrations increasing with decreasing pH. Increased temperature of incubation increased pH with a resultant decrease in the concentration of aluminium, but in one soil it appreciably increased the availability of iron in the early periods of incubation. Autumn and spring ploughing did not affect subsequent pH or the concentration of aluminium and iron in the soil solution. Manganese concentration varied from soil to soil and was not related to soil pH. In most soils there was a decrease in manganese concentration with length of incubation and it decreased more rapidly the lower the initial concentration. Temperature effects were variable and moisture affected the behaviour of manganese more than temperature. These findings and the distribution of aluminium, iron and manganese in the plant helped to explain the poor correlations.
- Full Text:
- Date Issued: 1969
- Authors: Ryding, William Wallace
- Date: 1969
- Subjects: Flue-cured tobacco -- Zimbabwe , Acid soils -- Zimbabwe
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4495 , http://hdl.handle.net/10962/d1013110
- Description: The main effects of lime, aluminium, iron and manganese were studied in field and greenhouse grown tobacco; relations between soil and plant measurements were examined. Ground limestone, ground mixed lime, ground dolomite and slaked lime at rates equivalent to 1,000 and 2,000 lb. CaC0₃/acre increased yield and quality of flue-cured tobacco both on Triassic and granite sands, whether applied early (February/March) or late (September); the highest rate and late application were often best. Yields increased with 4,000 and 6,000 lb. dolomite/acre applied late, but quality decreased when the pH was about 6.0. Lime did not affect leaf maturity as reflected by nitrogen and reducing sugars concentration . Where leaf discolouration (slate) occurred, the best quality and least discoloured leaf had the lowest manganese concentration and was grown on limed soil. On a very acid and probably nitrogen deficient soil, lime, borax and nitrogen (nitrate only tested) reduced the discolouration and improved the quality, but potassium sulphate increased discolouration and decreased quality. Calcium concentration in the leaf was increased by lime, particularly calcitic materials, and magnesium concentration was increased by dolomite. Lime also increased the filling value and petroleum ether extract, but decreased manganese, boron, chloride and sometimes potassium, and had no effect on phosphorus, nitrogen, aluminium, iron, crude fibre, nicotine, reducing sugars and equilibrium moisture. The inorganic composition of greenhouse plants was similar; generally gypsum increased calcium concentration more than calcium carbonate but it did not affect manganese concentration, which was decreased by calcium carbonate. In the stem and roots of field grown plants (dolomite only tested), the concentration of magnesium was increased but the concentrations of calcium, potassium, aluminium and iron were unaffected. Although the concentration of nitrogen was increased and that of phosphorus was decreased in the stem, these were unaffected in the roots. Aluminium and iron behaved differently to other nutrient ions, being more concentrated in the roots than aerial plant parts. Boron and magnesium deficiencies were observed in a dry and wet year, respectively, suggesting that variable mineral deficiencies can affect responses to lime. Initially soil pH was affected more by source of lime, but later mostly by rates. Slaked lime increased the soil pH more than did ground limestone, mixed lime or dolomite. In a glasshouse experiment, pH was more important than calcium supply and in the field, the largest yields were often associated with the highest pH. In pot experiments, aluminium drastically reduced yields in nutrient solution but not in soils, whereas iron was more severe in soils; manganese had little effect on yield. Manganese was readily taken up and translocated to the tops, but aluminium and iron were mainly concentrated in the roots, as was found in field grown plants. Iron decreased manganese concentration in all plant parts and aluminium decreased calcium and manganese in nutrient solution only. Although aluminium and iron generally increased the concentration of phosphorus in the roots, they did not interfere with phosphorus transport in the plant. Manganese caused the leaf to become chlorotic and when no iron was present the upper leaves became yellow, and developed brown and white lesions. However, in soil grown plants, sufficient iron was present in the soil solution to prevent break down of tissue. Yellowing of the upper leaves also occurred when plants were grown in nutrient solution with aluminium and no iron; when both were present, the plants were darker in colour. Although aluminium damaged roots in nutrient solution, high rates of iron severely damaged leaves of plants grown in soil. Since the concentrations of aluminium, iron and manganese were decreased in the soil solution by liming, they were compared with plant growth and composition in 17 different soils, with and without lime. As was expected, lime increased soil pH. It also increased exchangeable calcium, but decreased exchangeable aluminium, iron and manganese; exchangeable magnesium and potassium and resin extractable phosphorus were not affected. As the Ratio Law does not hold for all Rhodesian soils, anion adsorption will be avoided if the soils are equilibrated with O.OOOSM CaC1₂; the concentrations of the cations in solution were affected in the same way as exchangeable cations, but phosphorus was increased. There was no relationship between yield of tobacco and its chemical composition. The correlations between soil solution data and plant composition were poor, except for manganese and phosphorus; the relation between Mn ppm. in plant vsa (superscript)Mn/a (superscript)Ca + Mg (enclosed in square root sign √) in solution, and P% vs pH₂ P0₄ or pH₂ P0₄ +½ pCa, were both curvilinear. On the other hand, all measurements of exchangeable cations were poorly correlated with plant composition. Finally yield was poorly correlated with soil solution data, and pH was as satisfactory as any other measurement tested. Manganese toxicity was observed on three soils, and a probable manganese deficiency on one. It was not possible to define a limit above which manganese toxicity occurred, but manganese deficiency developed at about 63 ppm. manganese. Variations in pH and the availability of aluminium, iron and manganese occurred when soils were incubated at about field capacity, generally the main effects having developed within seven days. In all soils, there was an initial increase in soil pH and a maximum value was reached in one to four days, decreasing by variable amounts with longer periods of incubation. Although the concentration of aluminium was larger than that of iron, the relation between both ions and soil pH was curvilinear, their concentrations increasing with decreasing pH. Increased temperature of incubation increased pH with a resultant decrease in the concentration of aluminium, but in one soil it appreciably increased the availability of iron in the early periods of incubation. Autumn and spring ploughing did not affect subsequent pH or the concentration of aluminium and iron in the soil solution. Manganese concentration varied from soil to soil and was not related to soil pH. In most soils there was a decrease in manganese concentration with length of incubation and it decreased more rapidly the lower the initial concentration. Temperature effects were variable and moisture affected the behaviour of manganese more than temperature. These findings and the distribution of aluminium, iron and manganese in the plant helped to explain the poor correlations.
- Full Text:
- Date Issued: 1969
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