Synthetic and bioactivity studies of antiplasmodial and antibacterial marine natural products
- Authors: Young, Ryan Mark
- Date: 2012
- Subjects: Antibacterial agents Marine natural products Marine pharmacology Plasmodium falciparum Staphylococcus aureus Isocyanides Imidazoles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4378 , http://hdl.handle.net/10962/d1005043
- Description: This thesis is divided into two parts, assessing marine and synthetic compounds active firstly against Plasmodium falciparum (Chapter 3 and 4) and secondly active against methicillin resistant Staphylococcus aureus (MRSA, Chapter 5). In Chapter 3 the synthesis of nine new tricyclic podocarpanes (3.203-3.207 and 3.209-3.212) from the diterpene (+)-manool is described. Initial SAR study of synthetic podocarpanes concluded that the most active compound was a C-13 phenyl substituted podocarpane (3.204, IC₅₀ 6.6 μM). By preparing analogues with varying halogenated substituents on the phenyl ring (3.209-3.212) the antiplasmodial activity was improved (IC₅₀ 1.4 μM), while simultaneously decreasing the haemolysis previously reported for this class of compounds. Inspired by the antiplasmodial activity of Wright and Wattanapiromsakul’s tricycle marine isonitriles (2.16-2.21 and 2.24-2.27) an unsuccessfully attempt was made to convert tertiary alcohol moieties to isonitrile functionalities in compounds 3.188, 3.204-3.207 and 3.209-3.212. Over a decade ago Wright et al. proposed a putative antiplasmodial mechanism of action for marine isonitriles (2.4, 2.9, 2.15, 2.19 and 2.35) and isothiocyanate (2.34) which involved interference in haem detoxification by P. falciparum thus inhibiting the growth of the parasite. In Chapter 4 we describe how we successfully managed to scale down Egan’s β-haematin inhibition assay for the analyses of small quantities of marine natural products as potential β-haematin inhibitors. Our modified assay revealed that the most active antiplasmodial marine isonitrile 2.9 (IC₅₀ 13 nM) showed total β-haematin inhibition while 2.15 (IC₅₀ 81 nM) and 2.19 (IC₅₀ 31 nM) showed partial inhibition at three equivalents relative to haem. Using contempary molecular modelling techniques the charge on the isonitrile functionality was more accurately describe and the modified charge data sets was used to explore docking of marine isonitriles to haem using AutoDock. In Chapter 5 we describe how a lead South African marine bisindole MRSA pyruvate kinase inhibitor (5.8) was discovered in collaboration with colleagues at the University of British Columbia (UBC) and how this discovery inspired us to design a synthetic route to the dibrominated bisindole, isobromotopsentin (5.20) in an attempt to increase the bioactivity displayed by 5.8. We devised a fast and high yielding synthetic route using microwave assited organic synthesis. We first tested this synthesis using simple aryl glyoxals (5.27-5.32) as precursors to synthesize biphenylimidazoles (5.21-5.26), which later allowed us to synthesize the ascidian natural product 5.111. This method was sucessfully extended to the synthesis of deoxytopsentin (5.33) from an N-Boc protected indole methyl ketone (5.89). We subsequently were able to effectively remove the carbamate protection via thermal decomposition by heating the protected bisindole imidazole (5.90) in a microwave reactor for 5 min under argon. The synthesis of 5.20 resulted in an inseparable mixture of monoprotected and totally deprotected topsentin products, and due to time constraints we were not able to optimise this synthesis. Nonetheless our synthesis of the marine natural product 5.33 which was faster and higher yielding than previously reported routes could be extended to the synthesis of other topsentin bisindoles (5.138-5.140). Work towards this goal continues in our laboratory.
- Full Text:
- Date Issued: 2012
- Authors: Young, Ryan Mark
- Date: 2012
- Subjects: Antibacterial agents Marine natural products Marine pharmacology Plasmodium falciparum Staphylococcus aureus Isocyanides Imidazoles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4378 , http://hdl.handle.net/10962/d1005043
- Description: This thesis is divided into two parts, assessing marine and synthetic compounds active firstly against Plasmodium falciparum (Chapter 3 and 4) and secondly active against methicillin resistant Staphylococcus aureus (MRSA, Chapter 5). In Chapter 3 the synthesis of nine new tricyclic podocarpanes (3.203-3.207 and 3.209-3.212) from the diterpene (+)-manool is described. Initial SAR study of synthetic podocarpanes concluded that the most active compound was a C-13 phenyl substituted podocarpane (3.204, IC₅₀ 6.6 μM). By preparing analogues with varying halogenated substituents on the phenyl ring (3.209-3.212) the antiplasmodial activity was improved (IC₅₀ 1.4 μM), while simultaneously decreasing the haemolysis previously reported for this class of compounds. Inspired by the antiplasmodial activity of Wright and Wattanapiromsakul’s tricycle marine isonitriles (2.16-2.21 and 2.24-2.27) an unsuccessfully attempt was made to convert tertiary alcohol moieties to isonitrile functionalities in compounds 3.188, 3.204-3.207 and 3.209-3.212. Over a decade ago Wright et al. proposed a putative antiplasmodial mechanism of action for marine isonitriles (2.4, 2.9, 2.15, 2.19 and 2.35) and isothiocyanate (2.34) which involved interference in haem detoxification by P. falciparum thus inhibiting the growth of the parasite. In Chapter 4 we describe how we successfully managed to scale down Egan’s β-haematin inhibition assay for the analyses of small quantities of marine natural products as potential β-haematin inhibitors. Our modified assay revealed that the most active antiplasmodial marine isonitrile 2.9 (IC₅₀ 13 nM) showed total β-haematin inhibition while 2.15 (IC₅₀ 81 nM) and 2.19 (IC₅₀ 31 nM) showed partial inhibition at three equivalents relative to haem. Using contempary molecular modelling techniques the charge on the isonitrile functionality was more accurately describe and the modified charge data sets was used to explore docking of marine isonitriles to haem using AutoDock. In Chapter 5 we describe how a lead South African marine bisindole MRSA pyruvate kinase inhibitor (5.8) was discovered in collaboration with colleagues at the University of British Columbia (UBC) and how this discovery inspired us to design a synthetic route to the dibrominated bisindole, isobromotopsentin (5.20) in an attempt to increase the bioactivity displayed by 5.8. We devised a fast and high yielding synthetic route using microwave assited organic synthesis. We first tested this synthesis using simple aryl glyoxals (5.27-5.32) as precursors to synthesize biphenylimidazoles (5.21-5.26), which later allowed us to synthesize the ascidian natural product 5.111. This method was sucessfully extended to the synthesis of deoxytopsentin (5.33) from an N-Boc protected indole methyl ketone (5.89). We subsequently were able to effectively remove the carbamate protection via thermal decomposition by heating the protected bisindole imidazole (5.90) in a microwave reactor for 5 min under argon. The synthesis of 5.20 resulted in an inseparable mixture of monoprotected and totally deprotected topsentin products, and due to time constraints we were not able to optimise this synthesis. Nonetheless our synthesis of the marine natural product 5.33 which was faster and higher yielding than previously reported routes could be extended to the synthesis of other topsentin bisindoles (5.138-5.140). Work towards this goal continues in our laboratory.
- Full Text:
- Date Issued: 2012
Electrospun nanofibers : an alternative sorbent material for solid phase extraction
- Chigome, Samuel, Samuel Chigome
- Authors: Chigome, Samuel , Samuel Chigome
- Date: 2012 , 2012-03-26
- Subjects: Nanofibers -- Research Electrospinning -- Research Sorbents -- Research Extraction (Chemistry) -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4314 , http://hdl.handle.net/10962/d1004972
- Description: The work described in the thesis seeks to lay a foundation for a better understanding of the use of electrospun nanofibers as a sorbent material. Three miniaturised electrospun nanofiber based solid phase extraction devices were fabricated. For the first two, 10 mg of electrospun polystyrene fibers were used as a sorbent bed for a micro column SPE device (8 mm bed height in a 200 μl pipette tip) and a disk (I) SPE device (5 mm 1 mm sorbent bed in a 1000 μl SPE barrel). While for the third, 4.6 mg of electrospun nylon nanofibers were used as a sorbent bed for a disk (II) SPE device, (sorbent bed consisting of 5 5 mm 350 μm stacked disks in a 500 μl SPE barrel). Corticosteroids were employed as model analytes for performance evaluation of the fabricated SPE devices. Quantitative recoveries (45.5-124.29 percent) were achieved for all SPE devices at a loading volume of 100 μl and analyte concentration of 500 ng ml-1. Three mathematical models; the Boltzmann, Weibull five parameter and the Sigmoid three parameter were employed to describe the break through profiles of each of the sorbent beds. The micro column SPE device exhibited a breakthrough volume of 1400 μl, and theoretical plates (7.98-9.1) while disk (I) SPE device exhibited 400-500 μl and 1.39-2.82 respectively. Disk (II) SPE device exhibited a breakthrough volume of 200 μl and theoretical plates 0.38-1.15. It was proposed that the formats of future electrospun nanofiber sorbent based SPE devices will be guided by mechanical strength of the polymer. The study classified electrospun polymer fibers into two as polystyrene type (relatively low mechanical strength) and nylon type (relatively high mechanical strength).
- Full Text:
- Date Issued: 2012
- Authors: Chigome, Samuel , Samuel Chigome
- Date: 2012 , 2012-03-26
- Subjects: Nanofibers -- Research Electrospinning -- Research Sorbents -- Research Extraction (Chemistry) -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4314 , http://hdl.handle.net/10962/d1004972
- Description: The work described in the thesis seeks to lay a foundation for a better understanding of the use of electrospun nanofibers as a sorbent material. Three miniaturised electrospun nanofiber based solid phase extraction devices were fabricated. For the first two, 10 mg of electrospun polystyrene fibers were used as a sorbent bed for a micro column SPE device (8 mm bed height in a 200 μl pipette tip) and a disk (I) SPE device (5 mm 1 mm sorbent bed in a 1000 μl SPE barrel). While for the third, 4.6 mg of electrospun nylon nanofibers were used as a sorbent bed for a disk (II) SPE device, (sorbent bed consisting of 5 5 mm 350 μm stacked disks in a 500 μl SPE barrel). Corticosteroids were employed as model analytes for performance evaluation of the fabricated SPE devices. Quantitative recoveries (45.5-124.29 percent) were achieved for all SPE devices at a loading volume of 100 μl and analyte concentration of 500 ng ml-1. Three mathematical models; the Boltzmann, Weibull five parameter and the Sigmoid three parameter were employed to describe the break through profiles of each of the sorbent beds. The micro column SPE device exhibited a breakthrough volume of 1400 μl, and theoretical plates (7.98-9.1) while disk (I) SPE device exhibited 400-500 μl and 1.39-2.82 respectively. Disk (II) SPE device exhibited a breakthrough volume of 200 μl and theoretical plates 0.38-1.15. It was proposed that the formats of future electrospun nanofiber sorbent based SPE devices will be guided by mechanical strength of the polymer. The study classified electrospun polymer fibers into two as polystyrene type (relatively low mechanical strength) and nylon type (relatively high mechanical strength).
- Full Text:
- Date Issued: 2012
Synthesis and evaluation of novel HIV-1 enzyme inhibitors
- Olomola, Temitope Oloruntoba
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
- Full Text:
- Date Issued: 2011
- Authors: Olomola, Temitope Oloruntoba
- Date: 2011
- Subjects: HIV infections -- Treatment HIV infections -- Chemotherapy HIV (Viruses) Enzyme inhibitors AZT (Drug) Reverse transcriptase Proteolytic enzymes Ligands Psoralens Resorcinol
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4369 , http://hdl.handle.net/10962/d1005034
- Description: This study has involved the design, synthesis and evaluation of novel HIV-1 enzyme inhibitors accessed by synthetic elaboration of Baylis-Hillman adducts. Several series of complex coumarin-AZT and cinnamate ester-AZT conjugates have been prepared, in high yields, by exploiting the click reaction between appropriate Baylis-Hillman derived precursors and azidothymidine (AZT), all of which have been fully characterised using spectroscopic techniques. These conjugates, designed as potential dual-action HIV-1 inhibitors, were tested against the appropriate HIV-1 enzymes, i.e. HIV-1 reverse transcriptase and protease or HIV-1 reverse transcriptase and integrase. A number of the ligands have exhibited % inhibition levels and IC50 values comparable to drugs in clinical use, permitting their identification as lead compounds for the development of novel dual-action inhibitors. In silico docking of selected ligands into the active sites of the respective enzymes has provided useful insight into binding conformations and potential hydrogen-bonding interactions with active-site amino acid residues. A series of furocoumarin carboxamide derivatives have been synthesised in four steps starting from resorcinol and these compounds have also been tested for HIV-1 integrase inhibition activity. The structures of unexpected products isolated from Aza-Baylis-Hillman reactions of N-tosylaldimines have been elucidated by spectroscopic analysis, and confirmed by single crystal X-ray analysis. A mechanism for what appears to be an unprecedented transformation has been proposed. Microwave-assisted SeO₂ oxidation of Baylis-Hillman-derived 3-methylcoumarins has provided convenient and efficient access to coumarin-3-carbaldehydes, and a pilot study has revealed the potential of these coumarin-3-carbaldehydes as scaffolds for the construction of tricyclic compounds. The HCl-catalysed reaction of tert-butyl acrylate derived Baylis-Hillman adducts has been shown to afford 3-(chloromethyl)coumarins and α-(chloromethyl)cinnamic acids, the Zstereochemistry of the latter being established by X-ray crystallography. ¹H NMR-based experimental kinetic and DFT-level theoretical studies have been undertaken to establish the reaction sequence and other mechanistic details. Base-catalysed cyclisation on the other hand, has been shown to afford 2H-chromene rather than coumarin derivatives.
- Full Text:
- Date Issued: 2011
Photophysicochemical and photodynamic studies of phthalocyanines conjugated to selected drug delivery agents
- Authors: Nombona, Nolwazi
- Date: 2012
- Subjects: Phthalocyanines Photochemistry Photochemotherapy Drug delivery systems Magnesium Zinc Nanoparticles Staphylococcus aureus
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4333 , http://hdl.handle.net/10962/d1004994
- Description: This work reports on the successful synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines. The synthesis of symmetrical phthalocyanines is also reported. A selection of phthalocyanines have been conjugated, covalently linked, encapsulated or mixed with selected of drug delivery agents which include gold or silver nanoparticles, poly-L-lysine, liposomes and folic acid. The influence of delivery agent on the photophysical and photochemical properties of conjugated phthalocyanine is investigated. The studies showed that the Au nanoparticle significantly lowered the fluorescence quantum yield values of the phthalocyanines. The photodynamic activity of Zn phthalocyanine-ε-polylysine conjugates in the presence of nanoparticles towards the inactivation of Staphylococcus aureus showed high photoinactivation in the presence of silver nanoparticles. The presence of silver nanoparticels from the minimal inhibition concentration (MIC₅₀) studies showed remarkable growth inhibition for the tested conjugates even at low concentrations. The conjugate also showed no dark toxicity when evaluated using the chick choriallantoic membrane (CAM) assay. The efficiency of selected zinc phthalocyanine as photodynamic therapy (PDT) agents was investigated. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizers were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either gold nanoparticles or encapsulated in liposomes. Cell viability studies showed the optimum phototoxic effect on non-malignant cells to be 4.5 J.cm⁻². The PDT effect of the liposome bound phthalocyanine showed extensive damage of the breast cancer cells. Gold nanoparticles only showed a modest improvement in PDT activity.
- Full Text:
- Date Issued: 2012
- Authors: Nombona, Nolwazi
- Date: 2012
- Subjects: Phthalocyanines Photochemistry Photochemotherapy Drug delivery systems Magnesium Zinc Nanoparticles Staphylococcus aureus
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4333 , http://hdl.handle.net/10962/d1004994
- Description: This work reports on the successful synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines. The synthesis of symmetrical phthalocyanines is also reported. A selection of phthalocyanines have been conjugated, covalently linked, encapsulated or mixed with selected of drug delivery agents which include gold or silver nanoparticles, poly-L-lysine, liposomes and folic acid. The influence of delivery agent on the photophysical and photochemical properties of conjugated phthalocyanine is investigated. The studies showed that the Au nanoparticle significantly lowered the fluorescence quantum yield values of the phthalocyanines. The photodynamic activity of Zn phthalocyanine-ε-polylysine conjugates in the presence of nanoparticles towards the inactivation of Staphylococcus aureus showed high photoinactivation in the presence of silver nanoparticles. The presence of silver nanoparticels from the minimal inhibition concentration (MIC₅₀) studies showed remarkable growth inhibition for the tested conjugates even at low concentrations. The conjugate also showed no dark toxicity when evaluated using the chick choriallantoic membrane (CAM) assay. The efficiency of selected zinc phthalocyanine as photodynamic therapy (PDT) agents was investigated. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizers were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either gold nanoparticles or encapsulated in liposomes. Cell viability studies showed the optimum phototoxic effect on non-malignant cells to be 4.5 J.cm⁻². The PDT effect of the liposome bound phthalocyanine showed extensive damage of the breast cancer cells. Gold nanoparticles only showed a modest improvement in PDT activity.
- Full Text:
- Date Issued: 2012
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
Photophysical studies of Zinc phthalocyanine-silica nanoparticles conjugates
- Authors: Fashina, Adedayo
- Date: 2015
- Subjects: Nanoparticles , Phthalocyanines , Zinc , Silica , Photochemistry , Adsorption
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4537 , http://hdl.handle.net/10962/d1017917
- Description: This thesis reports on the synthesis and characterization of both symmetrical and asymmetrical Zinc phthalocyanine complexes. The complexes contained groups such as carboxylic, amino and alkyne for covalent grafting to the surface of silica nanoparticles. The use of symmetrical and asymmetrical complexes was geared towards comparing the non-specific binding of the symmetrical complexes to the specific binding observed in the asymmetrical complexes. The complexes were also doped within the silica matrix and compared to the surface grafted conjugates. The complexes and the conjugates were well characterized with a variety of techniques. The fluorescence lifetimes of the phthalocyanine complexes containing either terminal carboxylic groups or an alkyne group showed a mono-exponential decay while the amino containing phthalocyanine complexes gave a bi-exponential decay. A similar trend was observed for their respective conjugates. Some of the conjugates of the asymmetrical complexes showed a decrease in fluorescence lifetimes and a corresponding decrease in fluorescence quantum yields. The fluorescence quantum yields for all the symmetrical complexes studied showed either an improvement or retained the luminescence of the grafted phthalocyanine complex. Most of the conjugates showed a faster intersystem crossing time in comparison to the complexes alone. The grafted or doped conjugates containing symmetrical phthalocyanine complexes with carboxyl groups showed improvements both in fluorescence and triplet quantum yields. All the conjugates except two showed an increase in triplet lifetimes when compared to their respective phthalocyanine complexes. Optical nonlinearities of nine of the phthalocyanine complexes were studied and all the complexes showed characteristic reverse saturable absorption behavior. Complex 10 showed the most promising optical limiting behavior. The aggregation and dissolution studies of the conjugates were also carried out in a simulated biological medium and the silicon level detected was noticed to have increased with incubation time.
- Full Text:
- Date Issued: 2015
- Authors: Fashina, Adedayo
- Date: 2015
- Subjects: Nanoparticles , Phthalocyanines , Zinc , Silica , Photochemistry , Adsorption
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4537 , http://hdl.handle.net/10962/d1017917
- Description: This thesis reports on the synthesis and characterization of both symmetrical and asymmetrical Zinc phthalocyanine complexes. The complexes contained groups such as carboxylic, amino and alkyne for covalent grafting to the surface of silica nanoparticles. The use of symmetrical and asymmetrical complexes was geared towards comparing the non-specific binding of the symmetrical complexes to the specific binding observed in the asymmetrical complexes. The complexes were also doped within the silica matrix and compared to the surface grafted conjugates. The complexes and the conjugates were well characterized with a variety of techniques. The fluorescence lifetimes of the phthalocyanine complexes containing either terminal carboxylic groups or an alkyne group showed a mono-exponential decay while the amino containing phthalocyanine complexes gave a bi-exponential decay. A similar trend was observed for their respective conjugates. Some of the conjugates of the asymmetrical complexes showed a decrease in fluorescence lifetimes and a corresponding decrease in fluorescence quantum yields. The fluorescence quantum yields for all the symmetrical complexes studied showed either an improvement or retained the luminescence of the grafted phthalocyanine complex. Most of the conjugates showed a faster intersystem crossing time in comparison to the complexes alone. The grafted or doped conjugates containing symmetrical phthalocyanine complexes with carboxyl groups showed improvements both in fluorescence and triplet quantum yields. All the conjugates except two showed an increase in triplet lifetimes when compared to their respective phthalocyanine complexes. Optical nonlinearities of nine of the phthalocyanine complexes were studied and all the complexes showed characteristic reverse saturable absorption behavior. Complex 10 showed the most promising optical limiting behavior. The aggregation and dissolution studies of the conjugates were also carried out in a simulated biological medium and the silicon level detected was noticed to have increased with incubation time.
- Full Text:
- Date Issued: 2015
Synthesis and electrocatalytic properties of polymerizable metallophthalocyanines
- Authors: Obirai, Joseph Chinye
- Date: 2005
- Subjects: Phthalocyanines Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4447 , http://hdl.handle.net/10962/d1007733
- Description: The syntheses, spectral and electrochemical characterization of new family electropolymerizable pyrrole, thiophene and mercaptopyrimidin substituted metallophthalocyanine (MPc) complexes are described. Tetraamino substituted chromium and manganese phthalocyanine complexes were also synthesized and characterized. The spectral and electrochemical results are comparable to literature reports. The complexes formed stable films when deposited on electrode surfaces. The MPc films were formed by electropolymerization, drop-dry method and self-assembling. Nickel hydroxide-like electrodes were formed by electrotransformation of nickel-tetra-4- (pyrrol-1-yl)phenoxy phthalocyanine polymer films to the corresponding PcNi-O-NiPc modified electrodes in alkaline solution. The thiophene, mercaptopyrimidine functionalized MPcs and amino group containing complexes formed good self-assembled monolayers (SAMs) on gold electrode. The electrode modification processes were reproducible. The conductivities of the electrode were dependent on the surface concentrations of the complexes as a function of electropolymerization scan numbers. The electrodes showed good catalytic responses toward L-cysteine, nitrite, nitric oxide (NO), glycine, phenol and its derivative and oxygen. The results also suggest that the presence of thio groups on the ring substituents lowers the oxidation potential of Lcysteine more compared to literature values. The stability of the amperometric responses toward the various analytes is used to diagnose the applicability of the materials for electroanalytical purposes. The limits of detection for L-cysteine, nitrite, NO and glycine were in the range of ~10⁻⁷ to 10⁻⁵ mol dm⁻³.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph Chinye
- Date: 2005
- Subjects: Phthalocyanines Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4447 , http://hdl.handle.net/10962/d1007733
- Description: The syntheses, spectral and electrochemical characterization of new family electropolymerizable pyrrole, thiophene and mercaptopyrimidin substituted metallophthalocyanine (MPc) complexes are described. Tetraamino substituted chromium and manganese phthalocyanine complexes were also synthesized and characterized. The spectral and electrochemical results are comparable to literature reports. The complexes formed stable films when deposited on electrode surfaces. The MPc films were formed by electropolymerization, drop-dry method and self-assembling. Nickel hydroxide-like electrodes were formed by electrotransformation of nickel-tetra-4- (pyrrol-1-yl)phenoxy phthalocyanine polymer films to the corresponding PcNi-O-NiPc modified electrodes in alkaline solution. The thiophene, mercaptopyrimidine functionalized MPcs and amino group containing complexes formed good self-assembled monolayers (SAMs) on gold electrode. The electrode modification processes were reproducible. The conductivities of the electrode were dependent on the surface concentrations of the complexes as a function of electropolymerization scan numbers. The electrodes showed good catalytic responses toward L-cysteine, nitrite, nitric oxide (NO), glycine, phenol and its derivative and oxygen. The results also suggest that the presence of thio groups on the ring substituents lowers the oxidation potential of Lcysteine more compared to literature values. The stability of the amperometric responses toward the various analytes is used to diagnose the applicability of the materials for electroanalytical purposes. The limits of detection for L-cysteine, nitrite, NO and glycine were in the range of ~10⁻⁷ to 10⁻⁵ mol dm⁻³.
- Full Text:
- Date Issued: 2005
Nonlinear optical studies of phthalocyanines and their conjugates with nanomaterials
- Authors: Sanusi, Sikiru Olukayode
- Date: 2015
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4545 , http://hdl.handle.net/10962/d1017925
- Description: A number of metallophthalocyanines (MPcs) and metal-free phthalocyanines (H₂Pcs) have been synthesized and characterized using various characterization tools such as ¹H-NMR, TOF mass spectrometry, FT-IR, UV-visible spectrophotometry and CHNS elemental analysis. Some of the MPcs were covalently linked to nanomaterials such as silica nanoparticles (SiNPs), single-walled carbon nanotubes (SWCNTs), magnetite nanoparticles (MNPs) and quantum dots (QDs), or embedded in polymer thin-films using poly(methyl methacrylate) (PMMA) and poly(acrylic acid) (PAA) as the polymer sources. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), thermogravimetry analysis and X-ray diffractometry. The nonlinear optical (NLO) properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. In general, most of the investigated MPcs showed good optical limiting behaviors, except for a few, like the non-peripherally-substituted 2-pyridyloxy phthalocyanines, which showed inhibited NLO response as a result of the ring-strain effects. The absence of a metal center was found to greatly reduce the inherent high nonlinearities expected of some of the phthalocyanine complexes. The octaphenoxy derivatives (61a – 61e) were found to exhibit reverse saturable absorption (RSA) that depends on the singlet-singlet transitions, hence making them less reliable optical limiters. The optical limiting properties of the MPcs were improved in the presence of nanomaterials such as the QDs, MNPs and SWCNTs, with MPc-QDs showing the best optical limiting behavior of the three. SiNPs have no significant effect on the optical limiting behavior of the MPcs. The optical limiting properties of the MPcs were greatly enhanced in the presence of PMMA or PAA polymers. The PAA polymer showed better optical limiting behavior compared to PMMA
- Full Text:
- Date Issued: 2015
- Authors: Sanusi, Sikiru Olukayode
- Date: 2015
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4545 , http://hdl.handle.net/10962/d1017925
- Description: A number of metallophthalocyanines (MPcs) and metal-free phthalocyanines (H₂Pcs) have been synthesized and characterized using various characterization tools such as ¹H-NMR, TOF mass spectrometry, FT-IR, UV-visible spectrophotometry and CHNS elemental analysis. Some of the MPcs were covalently linked to nanomaterials such as silica nanoparticles (SiNPs), single-walled carbon nanotubes (SWCNTs), magnetite nanoparticles (MNPs) and quantum dots (QDs), or embedded in polymer thin-films using poly(methyl methacrylate) (PMMA) and poly(acrylic acid) (PAA) as the polymer sources. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), thermogravimetry analysis and X-ray diffractometry. The nonlinear optical (NLO) properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. In general, most of the investigated MPcs showed good optical limiting behaviors, except for a few, like the non-peripherally-substituted 2-pyridyloxy phthalocyanines, which showed inhibited NLO response as a result of the ring-strain effects. The absence of a metal center was found to greatly reduce the inherent high nonlinearities expected of some of the phthalocyanine complexes. The octaphenoxy derivatives (61a – 61e) were found to exhibit reverse saturable absorption (RSA) that depends on the singlet-singlet transitions, hence making them less reliable optical limiters. The optical limiting properties of the MPcs were improved in the presence of nanomaterials such as the QDs, MNPs and SWCNTs, with MPc-QDs showing the best optical limiting behavior of the three. SiNPs have no significant effect on the optical limiting behavior of the MPcs. The optical limiting properties of the MPcs were greatly enhanced in the presence of PMMA or PAA polymers. The PAA polymer showed better optical limiting behavior compared to PMMA
- Full Text:
- Date Issued: 2015
Measurements of the solubilities of some silver halides in water by electrical methods
- Authors: Malan, George McPherson
- Date: 1955
- Subjects: Silver halides -- Solubility , Silver halides -- Analysis , Conductometric analysis , Potentiometry , Silver halides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4515 , http://hdl.handle.net/10962/d1013502
- Description: [Introduction, p. 3] The solubilities of the silver halides cannot be determined by the conventional methods of analytical chemistry because they are too sparingly soluble (of the order 1 x 10⁻⁵ to 1 x 10⁻⁶ g . equiv./1. at 25°C.) However, electrical, and to a lesser extent optical methods, are admirably suited because of their greater sensitivity. The conductometric and potentiometric methods are the two most important electrical techniques for the measurement of the solubilities of sparingly soluble salts, and are the ones employed in this research. There are large discrepancies between the published values for the solubility of silver chloride. Results obtained by the conductometric and potentiometric methods disagree. In addition, figures quoted by independent authors using the same method differ by as much as 15%.
- Full Text:
- Date Issued: 1955
- Authors: Malan, George McPherson
- Date: 1955
- Subjects: Silver halides -- Solubility , Silver halides -- Analysis , Conductometric analysis , Potentiometry , Silver halides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4515 , http://hdl.handle.net/10962/d1013502
- Description: [Introduction, p. 3] The solubilities of the silver halides cannot be determined by the conventional methods of analytical chemistry because they are too sparingly soluble (of the order 1 x 10⁻⁵ to 1 x 10⁻⁶ g . equiv./1. at 25°C.) However, electrical, and to a lesser extent optical methods, are admirably suited because of their greater sensitivity. The conductometric and potentiometric methods are the two most important electrical techniques for the measurement of the solubilities of sparingly soluble salts, and are the ones employed in this research. There are large discrepancies between the published values for the solubility of silver chloride. Results obtained by the conductometric and potentiometric methods disagree. In addition, figures quoted by independent authors using the same method differ by as much as 15%.
- Full Text:
- Date Issued: 1955
The polysaccharides of Opuntia ficus-indica (L.) Mill. and Opuntia aurantiaca Lindl.
- Authors: McGarvie, Donald
- Date: 1977
- Subjects: Polysaccharides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4438 , http://hdl.handle.net/10962/d1007597
- Description: The partially acetylated acidic mucilage isolated from the cactus Opuntia ficus-indica consists of a highly branched molecule containing D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 2.9:6.6:3.8:1.3 : 1.0. A partial hydrolysis study led to the isolation of fourteen oligosaccharides and a degraded polysaccharide. Periodate oxidation of the degraded polysaccharide and methylation analysis of the degraded and reduced degraded polysaccharides led to the proposal of a structure for the degraded polysaccharide consisting of a chain of alternating α-l,4-D-galactopyranosyluronic acid and β-1,2-Lrhamnopyranosyl units with branches consisting of short chains of β-1,6-D-galactopyranosyl units Iinked to C-3 of the rhamnose residues. An insight into the nature of the peripheral side-chains was obtained by methylation studies of the oligosaccharides and the native polysaccharide. The majority of the side-chains are terminated by D-xylopyranosyl and L-arabinofuranosyl units while there is a small proportion of D-galactopyranosyl end-groups. The remaining units of the peripheral chains consists of mainly 1,3- and 1,5-1 inked L-arabinofuranosyl units. The acidic polysaccharide isolated from the jointed cactus Opuntia aurantiaca contains D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 5.9:5 .5:3.4: 1. 2:1.0 . A partial hydrolysis study revealed a similar series of galactose containing oligosaccharides as was identified from the mucilage of Opuntia ficus-indica. The degraded polysaccharide isolated from the partial hydrolysate was methylated and a possible structure proposed for the repeating unit. Methylation studies of the native polysaccharide indicated a polysaccharide with a more complex structure than that for the mucilage of Opuntia ficus-indica.
- Full Text:
- Date Issued: 1977
- Authors: McGarvie, Donald
- Date: 1977
- Subjects: Polysaccharides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4438 , http://hdl.handle.net/10962/d1007597
- Description: The partially acetylated acidic mucilage isolated from the cactus Opuntia ficus-indica consists of a highly branched molecule containing D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 2.9:6.6:3.8:1.3 : 1.0. A partial hydrolysis study led to the isolation of fourteen oligosaccharides and a degraded polysaccharide. Periodate oxidation of the degraded polysaccharide and methylation analysis of the degraded and reduced degraded polysaccharides led to the proposal of a structure for the degraded polysaccharide consisting of a chain of alternating α-l,4-D-galactopyranosyluronic acid and β-1,2-Lrhamnopyranosyl units with branches consisting of short chains of β-1,6-D-galactopyranosyl units Iinked to C-3 of the rhamnose residues. An insight into the nature of the peripheral side-chains was obtained by methylation studies of the oligosaccharides and the native polysaccharide. The majority of the side-chains are terminated by D-xylopyranosyl and L-arabinofuranosyl units while there is a small proportion of D-galactopyranosyl end-groups. The remaining units of the peripheral chains consists of mainly 1,3- and 1,5-1 inked L-arabinofuranosyl units. The acidic polysaccharide isolated from the jointed cactus Opuntia aurantiaca contains D-galactose, L-arabinose, D-xylose, D-galacturonic acid and L-rhamnose in the ratio 5.9:5 .5:3.4: 1. 2:1.0 . A partial hydrolysis study revealed a similar series of galactose containing oligosaccharides as was identified from the mucilage of Opuntia ficus-indica. The degraded polysaccharide isolated from the partial hydrolysate was methylated and a possible structure proposed for the repeating unit. Methylation studies of the native polysaccharide indicated a polysaccharide with a more complex structure than that for the mucilage of Opuntia ficus-indica.
- Full Text:
- Date Issued: 1977
Synthetic and physical organic studies of chromone derivatives
- Ramaite, Ipfani David Isaiah
- Authors: Ramaite, Ipfani David Isaiah
- Date: 1997
- Subjects: Benzopyrans Heterocyclic compounds -- Derivatives Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4380 , http://hdl.handle.net/10962/d1005045
- Description: A range of chromone-2-carboxylic acids has been prepared by condensing suitably substituted 2-hydroxyacetophenones with diethyl oxalate. pK₂ Studies of these acids revealed that 6- or 7-methoxy substituents decreased acidity while the 6-nitro group enhanced acidity; the strongest acid was the 3-chloro derivative, the increase in acidity being attributed to steric inhibition of acid-weakening delocalisation between the carboxyl group and the chromone system. Various chromone-2-carboxamides, derived from acid chloride precursors, were converted to polysubstituted acrylamides by nucleophilic ring-opening with selected amine nucleophiles. The main fragmentation patterns exhibited by these acrylamides were elucidated using a combination of low resolution, high resolution and meta-stable peak analysis, while the effect of substituents on the simultaneous internal rotation involving the carboxamide and enamine moieties were studied using dynamic NMR spectroscopy. Rotational barriers of ca. 67.1 kJmol ̄¹ and ca. 102 kJmol ̄¹ were found for the enamine and amide rotors, respectively. Several synthetic pathways were followed to prepare a series of 2-(N,N-dialkylamino)chromones which were subjected to detailed mass spectral analysis. In addition to substituent-specific fragmentations , the 2-aminochromones appear to fragment via 3 major pathways. The effect of substituents on the internal rotation of the amino moeity was investigated by variable temperature ¹H NMR spectroscopy and the resulting DNMR data was used to calculate the rotational barriers. Examination of the data reveals that the electron-releasing 6- and 7- substituents reduce the C-NMe₂ rotational barrier to ca. 43.5 kJmol ̄¹ , while the nitro analogue has the largest rotational barrier (ca. 46.1 kJmol ̄¹) because of the electron-withdrawing effect of this substituent.
- Full Text:
- Date Issued: 1997
- Authors: Ramaite, Ipfani David Isaiah
- Date: 1997
- Subjects: Benzopyrans Heterocyclic compounds -- Derivatives Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4380 , http://hdl.handle.net/10962/d1005045
- Description: A range of chromone-2-carboxylic acids has been prepared by condensing suitably substituted 2-hydroxyacetophenones with diethyl oxalate. pK₂ Studies of these acids revealed that 6- or 7-methoxy substituents decreased acidity while the 6-nitro group enhanced acidity; the strongest acid was the 3-chloro derivative, the increase in acidity being attributed to steric inhibition of acid-weakening delocalisation between the carboxyl group and the chromone system. Various chromone-2-carboxamides, derived from acid chloride precursors, were converted to polysubstituted acrylamides by nucleophilic ring-opening with selected amine nucleophiles. The main fragmentation patterns exhibited by these acrylamides were elucidated using a combination of low resolution, high resolution and meta-stable peak analysis, while the effect of substituents on the simultaneous internal rotation involving the carboxamide and enamine moieties were studied using dynamic NMR spectroscopy. Rotational barriers of ca. 67.1 kJmol ̄¹ and ca. 102 kJmol ̄¹ were found for the enamine and amide rotors, respectively. Several synthetic pathways were followed to prepare a series of 2-(N,N-dialkylamino)chromones which were subjected to detailed mass spectral analysis. In addition to substituent-specific fragmentations , the 2-aminochromones appear to fragment via 3 major pathways. The effect of substituents on the internal rotation of the amino moeity was investigated by variable temperature ¹H NMR spectroscopy and the resulting DNMR data was used to calculate the rotational barriers. Examination of the data reveals that the electron-releasing 6- and 7- substituents reduce the C-NMe₂ rotational barrier to ca. 43.5 kJmol ̄¹ , while the nitro analogue has the largest rotational barrier (ca. 46.1 kJmol ̄¹) because of the electron-withdrawing effect of this substituent.
- Full Text:
- Date Issued: 1997
An examination of the extractives of Leonotis species
- Authors: Kaplan, Errol R
- Date: 1966
- Subjects: Leonotis -- Analysis Botanical chemistry Chemistry, Analytic Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4481 , http://hdl.handle.net/10962/d1012628
- Description: Marrubiin and the other two diterpenoids, compounds X and Y, which had previously been isolated from Leonotus leonurus have been reinvestigated. Although the structure for marrubiin is well known its stereochemistry has been the subject of protracted discussion and is by no means secure except at C₅ and C₁₀ . N.M.R. spectral evidence showed that the lactone ring was cis-fused and β-orientated. Dehydration experiments carried out by previous workers were repeated, in order to resolve the residual uncertainty regarding the stereochemistry at C₉, an attempt was made to prepare iodoacetyl marrubic acid for X-ray crystallographic studies. Compound Y, C₂₀H₂₈0₃, a triply-unsaturated compound was shown by spectral studies to contain a furan ring and an α,β- unsaturated keto-group. It possesses a hydroxyl group incapable of acetylation, but readily removed by alkali and dehydrating agents to yield a tetraunsaturated compound, anhydro~Y; the hydroxyl is thus tertiary, Isolation of 1:2:5-trimethylnaphthalene on dehydrogenation indicated a relationship with the labdane diterpene group and supported the C₂₀ formula, The position of the α,β-unsaturated keto-group was resolved by interpretation of the ultraviolet spectra of degradation products and also by isolation of 1:2:3:5- trimethylnaphthalene on dehydrogenation of a suitable grignard product, The presence of a β-substituted furan was further indicated by colour reactions and confirmed by mass and n.m.r. spectra. The skeleton of compound Y is correlated with marrubiin via "iso-ambreinolide " and its stereochemistry is discussed. Further stereochemical assignments are postulated from the study of the n.m.r. spectra. Compound X, C₂₀H₂₈0₅, was shown by spectral and chemical evidence to be a diterpenoid dilactone containing an ether bridge between C₉ and C₁₃ Isolation of 1:2:5 trimethylnaphthal ene on dehydrogenation showed it to be closely related to marrubiin, This was supported by n.m.r. spectral results. A structure for compound X is proposed and the stereochemistry discussed. The aerial portions of Leonotis leonitis were also extracted and shown to contain a new compound, compound R. Preliminary investigation showed that it was a dilactone containing a furan ring, The n.m.r. spectrum of the compound is discussed.
- Full Text:
- Date Issued: 1966
- Authors: Kaplan, Errol R
- Date: 1966
- Subjects: Leonotis -- Analysis Botanical chemistry Chemistry, Analytic Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4481 , http://hdl.handle.net/10962/d1012628
- Description: Marrubiin and the other two diterpenoids, compounds X and Y, which had previously been isolated from Leonotus leonurus have been reinvestigated. Although the structure for marrubiin is well known its stereochemistry has been the subject of protracted discussion and is by no means secure except at C₅ and C₁₀ . N.M.R. spectral evidence showed that the lactone ring was cis-fused and β-orientated. Dehydration experiments carried out by previous workers were repeated, in order to resolve the residual uncertainty regarding the stereochemistry at C₉, an attempt was made to prepare iodoacetyl marrubic acid for X-ray crystallographic studies. Compound Y, C₂₀H₂₈0₃, a triply-unsaturated compound was shown by spectral studies to contain a furan ring and an α,β- unsaturated keto-group. It possesses a hydroxyl group incapable of acetylation, but readily removed by alkali and dehydrating agents to yield a tetraunsaturated compound, anhydro~Y; the hydroxyl is thus tertiary, Isolation of 1:2:5-trimethylnaphthalene on dehydrogenation indicated a relationship with the labdane diterpene group and supported the C₂₀ formula, The position of the α,β-unsaturated keto-group was resolved by interpretation of the ultraviolet spectra of degradation products and also by isolation of 1:2:3:5- trimethylnaphthalene on dehydrogenation of a suitable grignard product, The presence of a β-substituted furan was further indicated by colour reactions and confirmed by mass and n.m.r. spectra. The skeleton of compound Y is correlated with marrubiin via "iso-ambreinolide " and its stereochemistry is discussed. Further stereochemical assignments are postulated from the study of the n.m.r. spectra. Compound X, C₂₀H₂₈0₅, was shown by spectral and chemical evidence to be a diterpenoid dilactone containing an ether bridge between C₉ and C₁₃ Isolation of 1:2:5 trimethylnaphthal ene on dehydrogenation showed it to be closely related to marrubiin, This was supported by n.m.r. spectral results. A structure for compound X is proposed and the stereochemistry discussed. The aerial portions of Leonotis leonitis were also extracted and shown to contain a new compound, compound R. Preliminary investigation showed that it was a dilactone containing a furan ring, The n.m.r. spectrum of the compound is discussed.
- Full Text:
- Date Issued: 1966
Applications of the Baylis-Hillman reaction in the synthesis of coumarin derivatives
- Authors: Musa, Musiliyu Ayodele
- Date: 2003
- Subjects: Coumarins Heterocyclic compounds -- Derivatives
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4403 , http://hdl.handle.net/10962/d1006705
- Description: The reaction of specially prepared salicylaldehyde benzyl ethers with the activated alkenes, methyl acrylate or acrylonitrile, in the presence of the catalyst, DABCO, has afforded Baylis-Hillman products, which have been subjected to conjugate addition with either piperidine or benzylamine. Hydrogenolysis of these conjugate addition products in the presence of a palladium-on-carbon catalyst has been shown to afford the corresponding 3-substituted coumarins, while treatment of O-benzylated Baylis-Hillman adducts with HCl or HI afforded the corresponding 3-(halomethyl)coumarins directly, in up to 94%. The 3-(halomethyl)coumarins have also been obtained in excellent yields (up to 98%) and even more conveniently, by treating the unprotected Baylis-Hillman products with HCl in a mixture of AcOH and Ac₂O, obtained from tert-butyl acrylate and various salicylaldehydes. The generality of an established route to the synthesis of coumarins via an intramolecular Baylis-Hillman reaction, involving the use of salicylaldehyde acrylate esters in the presence of DABCO, has also been demonstrated. Reactions between the 3-(halomethyl)coumarins and various nitrogen and carbon nucleophiles have been shown to proceed with a high degree of regioselectivity at the exocyclic allylic centre to afford 3-substituted coumarin products. The electronimpact mass spectra of selected coumarin derivatives have been investigated using high-resolution and B/E linked scan data. Fragmentation pathways have been proposed and fragmentation modes associated with different coumarin-containing analogues have been compared. A series of coumarin-containing analogues of ritonavir (a clinically useful HIV-1 protease inhibitor) have been prepared and characterized. The synthetic approach has involved the coupling of coumarin derivatives with a hydroxyethylene dipeptide isostere to afford ritonavir analogues containing coumarin termini. An interactive docking procedure has been used to explore the docking of ritonavir and a coumarincontaining analogue into the enzyme active site.
- Full Text:
- Date Issued: 2003
- Authors: Musa, Musiliyu Ayodele
- Date: 2003
- Subjects: Coumarins Heterocyclic compounds -- Derivatives
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4403 , http://hdl.handle.net/10962/d1006705
- Description: The reaction of specially prepared salicylaldehyde benzyl ethers with the activated alkenes, methyl acrylate or acrylonitrile, in the presence of the catalyst, DABCO, has afforded Baylis-Hillman products, which have been subjected to conjugate addition with either piperidine or benzylamine. Hydrogenolysis of these conjugate addition products in the presence of a palladium-on-carbon catalyst has been shown to afford the corresponding 3-substituted coumarins, while treatment of O-benzylated Baylis-Hillman adducts with HCl or HI afforded the corresponding 3-(halomethyl)coumarins directly, in up to 94%. The 3-(halomethyl)coumarins have also been obtained in excellent yields (up to 98%) and even more conveniently, by treating the unprotected Baylis-Hillman products with HCl in a mixture of AcOH and Ac₂O, obtained from tert-butyl acrylate and various salicylaldehydes. The generality of an established route to the synthesis of coumarins via an intramolecular Baylis-Hillman reaction, involving the use of salicylaldehyde acrylate esters in the presence of DABCO, has also been demonstrated. Reactions between the 3-(halomethyl)coumarins and various nitrogen and carbon nucleophiles have been shown to proceed with a high degree of regioselectivity at the exocyclic allylic centre to afford 3-substituted coumarin products. The electronimpact mass spectra of selected coumarin derivatives have been investigated using high-resolution and B/E linked scan data. Fragmentation pathways have been proposed and fragmentation modes associated with different coumarin-containing analogues have been compared. A series of coumarin-containing analogues of ritonavir (a clinically useful HIV-1 protease inhibitor) have been prepared and characterized. The synthetic approach has involved the coupling of coumarin derivatives with a hydroxyethylene dipeptide isostere to afford ritonavir analogues containing coumarin termini. An interactive docking procedure has been used to explore the docking of ritonavir and a coumarincontaining analogue into the enzyme active site.
- Full Text:
- Date Issued: 2003
Sample preparation for pesticide analysis in water and sediments a case study of the Okavango Delta, Botswana
- Authors: Mmualefe, Lesego Cecilia
- Date: 2010
- Subjects: Water quality -- Botswana -- Okavango Delta Water -- Analysis Pesticides -- Environmental aspects -- Botswana -- Okavango Delta Water -- Pollution -- Botswana -- Okavango Delta DDT (Insecticide) -- Environmental aspects -- Botswana -- Okavango Delta
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4344 , http://hdl.handle.net/10962/d1005006
- Description: This thesis presents a first ever extensive analysis of pesticides in water and sediments from the Okavango Delta, Botswana, employing green sample preparation techniques that require small volumes of organic solvents hence generating negligible volumes of organic solvent waste. Pesticides were extracted and pre-concentrated from water by solid phase extraction (SPE) and headspace solid phase microextraction (HS-SPME) while supercritical fluid extraction (SFE) and pressurized fluid extraction (PFE) were employed for sediments. Subsequent analysis was carried out on a gas chromatograph with electron capture detection and analytes were unequivocally confirmed by high resolution mass spectrometric detection. Hexachlorobenzene (HCB), trans-chlordane, 4,4′-DDD and 4,4′-DDE were detected after optimized HS-SPME in several water samples from the lower Delta at concentrations ranging from 2.4 to 61.4 μg L-1 that are much higher than the 0.1 μg L-1 maximum limit of individual organochlorine pesticides in drinking water set by the European Community Directive. The same samples were cleaned with ISOLUTE C18 SPE sorbent with an optimal acetone/n-hexane (1:1 v/v) mixture for the elution of analytes. No pesticides were detected after SPE clean-up and pre-concentration. HCB, aldrin and 4, 4‟-DDT were identified in sediments after SFE at concentration ranges of 1.1 - 30.3, 0.5 – 15.2 and 1.4 – 55.4 μg/g, respectively. There was an increase of pesticides concentrations in the direction of water flow from the Panhandle (point of entry) to the lower delta. DDE, fatty acids and phthalates were detected after PFE with optimized extraction solvent and temperature. The presence of DDT metabolites in the water and sediments from the Okavango Delta confirm historical exposure to the pesticide. However their cumulative concentration increase in the water-flow direction calls for further investigation of point sources for the long-term preservation of the Delta. The green sample preparation techniques and low toxicity solvents employed in this thesis are thus recommended for routine environmental monitoring exercises.
- Full Text:
- Date Issued: 2010
- Authors: Mmualefe, Lesego Cecilia
- Date: 2010
- Subjects: Water quality -- Botswana -- Okavango Delta Water -- Analysis Pesticides -- Environmental aspects -- Botswana -- Okavango Delta Water -- Pollution -- Botswana -- Okavango Delta DDT (Insecticide) -- Environmental aspects -- Botswana -- Okavango Delta
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4344 , http://hdl.handle.net/10962/d1005006
- Description: This thesis presents a first ever extensive analysis of pesticides in water and sediments from the Okavango Delta, Botswana, employing green sample preparation techniques that require small volumes of organic solvents hence generating negligible volumes of organic solvent waste. Pesticides were extracted and pre-concentrated from water by solid phase extraction (SPE) and headspace solid phase microextraction (HS-SPME) while supercritical fluid extraction (SFE) and pressurized fluid extraction (PFE) were employed for sediments. Subsequent analysis was carried out on a gas chromatograph with electron capture detection and analytes were unequivocally confirmed by high resolution mass spectrometric detection. Hexachlorobenzene (HCB), trans-chlordane, 4,4′-DDD and 4,4′-DDE were detected after optimized HS-SPME in several water samples from the lower Delta at concentrations ranging from 2.4 to 61.4 μg L-1 that are much higher than the 0.1 μg L-1 maximum limit of individual organochlorine pesticides in drinking water set by the European Community Directive. The same samples were cleaned with ISOLUTE C18 SPE sorbent with an optimal acetone/n-hexane (1:1 v/v) mixture for the elution of analytes. No pesticides were detected after SPE clean-up and pre-concentration. HCB, aldrin and 4, 4‟-DDT were identified in sediments after SFE at concentration ranges of 1.1 - 30.3, 0.5 – 15.2 and 1.4 – 55.4 μg/g, respectively. There was an increase of pesticides concentrations in the direction of water flow from the Panhandle (point of entry) to the lower delta. DDE, fatty acids and phthalates were detected after PFE with optimized extraction solvent and temperature. The presence of DDT metabolites in the water and sediments from the Okavango Delta confirm historical exposure to the pesticide. However their cumulative concentration increase in the water-flow direction calls for further investigation of point sources for the long-term preservation of the Delta. The green sample preparation techniques and low toxicity solvents employed in this thesis are thus recommended for routine environmental monitoring exercises.
- Full Text:
- Date Issued: 2010
A bioinorganic study of some cobalt(II) Schiff base complexes of variously substituted hydroxybenzaldimines
- Authors: Shaibu, Rafiu Olarewaju
- Date: 2008
- Subjects: Cobalt Schiff bases Artemia Spectrum analysis Ligands -- Analysis Bioinorganic chemistry Antineoplastic agents Cancer -- Chemotherapy Ligands -- Toxicity
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4394 , http://hdl.handle.net/10962/d1006009
- Description: Syntheses of Schiff bases were carried out by reacting salicylaldyhde, ortho-vanillin, para-vanillin or vanillin with aniline, 1-aminonaphthalene, 4- and 3-aminopyridine, and also with 2- and 3-aminomethylpyridine. The various Schiff bases obtained from the condensation reaction were reacted with CoCl₂.6H₂0, triethylamine stripped CoCl₂.6H₂0 or Co(CH₃COO)₂ to form cobalt(Il) complexes of ratio 2:1. The complexes obtained from cobalt chloride designated as the "A series" are of the general formulae ML₂X₂.nH₂0 , (L = Schiff base, X = chlorine) while those obtained from cobalt acetate or triethylamine stripped cobalt chloride denoted as "B" and C" are of the general formulae ML₂. nH₂0. The few complexes that do not follow the general formulae highlighted above are: IA [M(HL)₃.Cl₂], (L = N-phenylsalicylaldimine), 4A = (MLCl₂), (L = N-phenylvanaldiminato), 7 A and 21 A (ML₂), (L = N-naphthyl-o-vanaldiminato, and N-methy-2-pyridylsalicylaldiminato respectively), 8A = MLCI, (L = N-naphthylvanaldiminato), 12A = M₂L₃Cl₂, (L = N-4-pyridylvanaldiminato), 15A (MLCI), (L = N-3-pyridyl-o-vanaldiminato). The ligands and their complexes were characterized using elemental analyses and cobalt analysis using ICP, FT-IR spectroscopy (mid and far-IR), NIR-UV/vis (diffuse reflectance), UV/vis in an aprotic and a protic solvents, while mass spectrometry, ¹HNMR and ¹³CNMR, was used to further characterized the ligands. The tautomeric nature of the Schiff bases were determined by examining the behaviour of Schiff bases and their complexes in a protic (e.g. MeOH) and non-protic (e.g. DMF) polar solvents. The effects of solvents on the electronic behaviour of the compounds were also examined. Using CDCl₃, the NMR technique was further used to confirm the structures of the Schiff bases. The tentative geometry of the complexes was determined using the spectra information obtained from the far infrared and the diffuse reflectance spectroscopy. With few exceptions, most of the "A" series are tetrahedral or distorted tetrahedral, while the "B + C" are octahedral or pseudooctahedral. A small number of complexes are assigned square-planar geometry owing to the characteristic spectral behaviour shown. In order to determine their biological activity, two biological assay methods (antimicrobial testing and brine shrimp lethality assay) were used. Using disc method, the bacteriostatic and fungicidal activities of the various Schiff bases and their respective complexes to Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa as well as Aspergillus niger, were measured and the average inhibition zones are tabulated and analysed. Both the Schiff bases and their complexes showed varying bacteriostatic and fungicidal activity against the bacteria and fungus tested. The inhibition activity is concentration dependent and potential antibiotic and fungicides are identified. To determine the toxicity of the ligands and their corresponding cobalt(II) complexes, brine shrimp lethality assay was used. The LD₅₀ of the tested compounds were calculated and the results obtained were tabulated for comparison.
- Full Text:
- Date Issued: 2008
- Authors: Shaibu, Rafiu Olarewaju
- Date: 2008
- Subjects: Cobalt Schiff bases Artemia Spectrum analysis Ligands -- Analysis Bioinorganic chemistry Antineoplastic agents Cancer -- Chemotherapy Ligands -- Toxicity
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4394 , http://hdl.handle.net/10962/d1006009
- Description: Syntheses of Schiff bases were carried out by reacting salicylaldyhde, ortho-vanillin, para-vanillin or vanillin with aniline, 1-aminonaphthalene, 4- and 3-aminopyridine, and also with 2- and 3-aminomethylpyridine. The various Schiff bases obtained from the condensation reaction were reacted with CoCl₂.6H₂0, triethylamine stripped CoCl₂.6H₂0 or Co(CH₃COO)₂ to form cobalt(Il) complexes of ratio 2:1. The complexes obtained from cobalt chloride designated as the "A series" are of the general formulae ML₂X₂.nH₂0 , (L = Schiff base, X = chlorine) while those obtained from cobalt acetate or triethylamine stripped cobalt chloride denoted as "B" and C" are of the general formulae ML₂. nH₂0. The few complexes that do not follow the general formulae highlighted above are: IA [M(HL)₃.Cl₂], (L = N-phenylsalicylaldimine), 4A = (MLCl₂), (L = N-phenylvanaldiminato), 7 A and 21 A (ML₂), (L = N-naphthyl-o-vanaldiminato, and N-methy-2-pyridylsalicylaldiminato respectively), 8A = MLCI, (L = N-naphthylvanaldiminato), 12A = M₂L₃Cl₂, (L = N-4-pyridylvanaldiminato), 15A (MLCI), (L = N-3-pyridyl-o-vanaldiminato). The ligands and their complexes were characterized using elemental analyses and cobalt analysis using ICP, FT-IR spectroscopy (mid and far-IR), NIR-UV/vis (diffuse reflectance), UV/vis in an aprotic and a protic solvents, while mass spectrometry, ¹HNMR and ¹³CNMR, was used to further characterized the ligands. The tautomeric nature of the Schiff bases were determined by examining the behaviour of Schiff bases and their complexes in a protic (e.g. MeOH) and non-protic (e.g. DMF) polar solvents. The effects of solvents on the electronic behaviour of the compounds were also examined. Using CDCl₃, the NMR technique was further used to confirm the structures of the Schiff bases. The tentative geometry of the complexes was determined using the spectra information obtained from the far infrared and the diffuse reflectance spectroscopy. With few exceptions, most of the "A" series are tetrahedral or distorted tetrahedral, while the "B + C" are octahedral or pseudooctahedral. A small number of complexes are assigned square-planar geometry owing to the characteristic spectral behaviour shown. In order to determine their biological activity, two biological assay methods (antimicrobial testing and brine shrimp lethality assay) were used. Using disc method, the bacteriostatic and fungicidal activities of the various Schiff bases and their respective complexes to Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa as well as Aspergillus niger, were measured and the average inhibition zones are tabulated and analysed. Both the Schiff bases and their complexes showed varying bacteriostatic and fungicidal activity against the bacteria and fungus tested. The inhibition activity is concentration dependent and potential antibiotic and fungicides are identified. To determine the toxicity of the ligands and their corresponding cobalt(II) complexes, brine shrimp lethality assay was used. The LD₅₀ of the tested compounds were calculated and the results obtained were tabulated for comparison.
- Full Text:
- Date Issued: 2008
Continuous-flow dynamic dialysis and its application to collagen-ligand interactions
- Authors: Sparrow, Neil Arthur
- Date: 1983
- Subjects: Collagen Ligands (Biochemistry) Ligand binding (Biochemistry) Protein-protein interactions Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4297 , http://hdl.handle.net/10962/d1004617
- Description: Studies undertaken to investigate the binding of low molecular mass analogues of polyphenolic vegetable tannins to collagen have prompted the development of a new method to investigate protein-ligand interactions. This method, the continuous-flow dynamic dialysis method (CFDD), differs from conventional dialysis procedures used for protein-ligand binding studies. In this method, the ligand concentration in the diffusate is monitored automatically at successive closely spaced time intervals while being continuously eluted from the dialysis cell. The primary data obtained by this method consists of a series of spectrophotometric absorbance measurements representing the ligand concentration in the sink compartment of a dialysis cell. This primary data is recorded by means of a data logging device onto a punched paper tape for subsequent computer processing. Two original methods are presented for analysing the primary data to extract the protein-ligand binding isotherm. The first of these is a direct analysis which relies on Fick's first law of diffusion. In this method it is necessary to establish, by means of a control experiment, a value for the ligand permeation constant. This is used in a subsequent analysis to establish a relationship between the measured rate of diffusion of the ligand from a protein-ligand mixture and the concentration of unbound ligand which is in equilibrium with the protein-ligand complex. The protein-ligand binding isotherm is obtained from parametric equations which give the quantity of ligand bound to the protein and the concentration of unbound ligand in the sample compartment as functions of time. The second method, which is more general, utilizes the same primary data but is based on establishing a system transfer function to characterise the dialysis and eluting processes. This analysis depends on the linearity of the system and utilizes numerical laplace transforms of the primary data sets obtained from control and protein-ligand dialyses. Laplace transforms are used to effect a deconvolution of the transfer function from the primary data and yield the concentration of ligand in equilibrium with the protein-ligand complex. This procedure yields, simultaneously, both the total ligand concentration and the concentration of unbound ligand in the protein compartment of the dialysis cell. These quantities are used to establish the binding isotherm for the protein ligand system. Numerical inversion of the laplace transforms in this analysis is effected by their reduction to Fourier series. The experimental reliability of the continuous-flow dynamic dialysis method, and validity of the two analytical methods used to derive a binding isotherm from dialysis data are evaluated from studies of the binding of phenol red to bovine serum albumin (BSA) at 15⁰, 20⁰ and 25⁰ C, as well as from simulated binding curves generated by the numerical solution of the differential equations used to describe the dialysis and elution process in terms of a two-site Scatchard binding model. The method is used to investigate the binding to collagen of a series of low molecular mass phenolic compounds which can be isolated from Wattle and Quebracho vegetable tannin extracts. These compounds can be considered as monomeric precursor analogues of the polymeric vegetable tannins. The binding of these ligands to collagen is shown to be characterised by high capacity, low affinity binding in which the uptake of ligand by the protein increases linearly with increasing ligand concentration. Collagen exhibits no indication of site saturation for these ligands over the experimentally accessible concentration ranges investigated.
- Full Text:
- Date Issued: 1983
- Authors: Sparrow, Neil Arthur
- Date: 1983
- Subjects: Collagen Ligands (Biochemistry) Ligand binding (Biochemistry) Protein-protein interactions Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4297 , http://hdl.handle.net/10962/d1004617
- Description: Studies undertaken to investigate the binding of low molecular mass analogues of polyphenolic vegetable tannins to collagen have prompted the development of a new method to investigate protein-ligand interactions. This method, the continuous-flow dynamic dialysis method (CFDD), differs from conventional dialysis procedures used for protein-ligand binding studies. In this method, the ligand concentration in the diffusate is monitored automatically at successive closely spaced time intervals while being continuously eluted from the dialysis cell. The primary data obtained by this method consists of a series of spectrophotometric absorbance measurements representing the ligand concentration in the sink compartment of a dialysis cell. This primary data is recorded by means of a data logging device onto a punched paper tape for subsequent computer processing. Two original methods are presented for analysing the primary data to extract the protein-ligand binding isotherm. The first of these is a direct analysis which relies on Fick's first law of diffusion. In this method it is necessary to establish, by means of a control experiment, a value for the ligand permeation constant. This is used in a subsequent analysis to establish a relationship between the measured rate of diffusion of the ligand from a protein-ligand mixture and the concentration of unbound ligand which is in equilibrium with the protein-ligand complex. The protein-ligand binding isotherm is obtained from parametric equations which give the quantity of ligand bound to the protein and the concentration of unbound ligand in the sample compartment as functions of time. The second method, which is more general, utilizes the same primary data but is based on establishing a system transfer function to characterise the dialysis and eluting processes. This analysis depends on the linearity of the system and utilizes numerical laplace transforms of the primary data sets obtained from control and protein-ligand dialyses. Laplace transforms are used to effect a deconvolution of the transfer function from the primary data and yield the concentration of ligand in equilibrium with the protein-ligand complex. This procedure yields, simultaneously, both the total ligand concentration and the concentration of unbound ligand in the protein compartment of the dialysis cell. These quantities are used to establish the binding isotherm for the protein ligand system. Numerical inversion of the laplace transforms in this analysis is effected by their reduction to Fourier series. The experimental reliability of the continuous-flow dynamic dialysis method, and validity of the two analytical methods used to derive a binding isotherm from dialysis data are evaluated from studies of the binding of phenol red to bovine serum albumin (BSA) at 15⁰, 20⁰ and 25⁰ C, as well as from simulated binding curves generated by the numerical solution of the differential equations used to describe the dialysis and elution process in terms of a two-site Scatchard binding model. The method is used to investigate the binding to collagen of a series of low molecular mass phenolic compounds which can be isolated from Wattle and Quebracho vegetable tannin extracts. These compounds can be considered as monomeric precursor analogues of the polymeric vegetable tannins. The binding of these ligands to collagen is shown to be characterised by high capacity, low affinity binding in which the uptake of ligand by the protein increases linearly with increasing ligand concentration. Collagen exhibits no indication of site saturation for these ligands over the experimentally accessible concentration ranges investigated.
- Full Text:
- Date Issued: 1983
Design, synthesis and evaluation of silver-specific ligands
- Authors: Daubinet, André
- Date: 2001
- Subjects: Ligands Ligands -- Design Ligands -- Analysis Ligands -- Evaluation Silver -- Metallurgy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4308 , http://hdl.handle.net/10962/d1004966
- Description: Several series of ligands, designed to chelate silver(I) specifically in the presence of base metals, have been synthesised. The ligands include: - dithiodiamide compounds, prepared by the condensation of acetanilide derivatives with 1,2-dibromoethane; propanenitrile and propanoic ester derivatives prepared from pyridine-2-carbaldehyde via the Morita-Baylis-Hillman reaction; and novel malonamide ligands from the reaction of diethyl malonate with a range of primary amines. The malonamide derivatives were prepared under both conventional thermal and microwave-assisted conditions, the latter proving to be highly efficient. The ligands were all characterised using a combination of spectroscopic and, where appropriate, elemental analysis; in one case, the structural assignment was confirmed by single-crystal X-ray analysis. The fragmentation patterns in the electron-impact mass spectra of the malonamide derivatives have been explored using high-resolution and meta-stable peak scanning techniques. Complexes of the malonamide ligands with copper(II) and silver(I) have been synthesised, and examination of these complexes has revealed distinct differences in their co-ordination preferences towards silver(I) and copper(II). Tentative, computer-modelled structures for the complexes have been proposed using the available spectroscopic and elemental analysis data. Computer modelling, at the Molecular Mechanics level, has also been used to assess the capacity of the ligand systems to adopt conformations suitable for the chelation of tetrahedral silver(I). Solvent extraction studies have been undertaken using aqueous metal ion solutions and various organic solvents. The dithiodiamide derivatives typically presented solubility problems, but one of the ligands, N,N´-bis(3-chlorophenyl)-3,6-dithiaoctanediamide, exhibited significant but slow extraction of silver(I) into toluene. The malonamide derivatives, however, proved to be readily soluble in ethyl acetate and, in some cases, exhibited good to excellent selectivity for silver(I) in the presence of the base metals copper and lead. Atomic absorption analysis revealed rapid equilibration times (<15 min) and high extraction efficiencies over a wide pH range (2.78 - 9.0). Metal selectivity has been determined by ICP-MS analysis of the residual silver, copper and lead present in the aqueous phase after 15 min, and one of the ligands, N,N´-bis(2-benzylsulfanylethyl)malonamide, exhibits excellent (≥ 96 %) silver(I) specificity.
- Full Text:
- Date Issued: 2001
- Authors: Daubinet, André
- Date: 2001
- Subjects: Ligands Ligands -- Design Ligands -- Analysis Ligands -- Evaluation Silver -- Metallurgy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4308 , http://hdl.handle.net/10962/d1004966
- Description: Several series of ligands, designed to chelate silver(I) specifically in the presence of base metals, have been synthesised. The ligands include: - dithiodiamide compounds, prepared by the condensation of acetanilide derivatives with 1,2-dibromoethane; propanenitrile and propanoic ester derivatives prepared from pyridine-2-carbaldehyde via the Morita-Baylis-Hillman reaction; and novel malonamide ligands from the reaction of diethyl malonate with a range of primary amines. The malonamide derivatives were prepared under both conventional thermal and microwave-assisted conditions, the latter proving to be highly efficient. The ligands were all characterised using a combination of spectroscopic and, where appropriate, elemental analysis; in one case, the structural assignment was confirmed by single-crystal X-ray analysis. The fragmentation patterns in the electron-impact mass spectra of the malonamide derivatives have been explored using high-resolution and meta-stable peak scanning techniques. Complexes of the malonamide ligands with copper(II) and silver(I) have been synthesised, and examination of these complexes has revealed distinct differences in their co-ordination preferences towards silver(I) and copper(II). Tentative, computer-modelled structures for the complexes have been proposed using the available spectroscopic and elemental analysis data. Computer modelling, at the Molecular Mechanics level, has also been used to assess the capacity of the ligand systems to adopt conformations suitable for the chelation of tetrahedral silver(I). Solvent extraction studies have been undertaken using aqueous metal ion solutions and various organic solvents. The dithiodiamide derivatives typically presented solubility problems, but one of the ligands, N,N´-bis(3-chlorophenyl)-3,6-dithiaoctanediamide, exhibited significant but slow extraction of silver(I) into toluene. The malonamide derivatives, however, proved to be readily soluble in ethyl acetate and, in some cases, exhibited good to excellent selectivity for silver(I) in the presence of the base metals copper and lead. Atomic absorption analysis revealed rapid equilibration times (<15 min) and high extraction efficiencies over a wide pH range (2.78 - 9.0). Metal selectivity has been determined by ICP-MS analysis of the residual silver, copper and lead present in the aqueous phase after 15 min, and one of the ligands, N,N´-bis(2-benzylsulfanylethyl)malonamide, exhibits excellent (≥ 96 %) silver(I) specificity.
- Full Text:
- Date Issued: 2001
Structural and synthetic investigations of diterpenoid natural products from southern African marine invertebrates
- Authors: Gray, Christopher Anthony
- Date: 2003
- Subjects: Ethyl acetoacetate Diterpenes Limpets -- South Africa Natural products -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4349 , http://hdl.handle.net/10962/d1005014
- Description: This thesis is divided into two parts. The first part (Chapter Two) documents a bioassay guided investigation of the ethyl acetate extracts of four marine invertebrates from Mozambique (an Irciniid sponge, a Haliclona sp. sponge, an ascidian tentatively identified as Diplosoma sp., and the soft coral Cladiella kashmani). Eight known compounds [ilimaquinone (2.1), renierone (2.7), N-formyl-1,2-dihydrorenierone (2.8), 1,6-dimethyl-7-methoxy-5,8-dihydroisoquinoline-5,8-dione (2.9), mimosamycin (2.10) 7Z-allylidene-5-hydroxy-7,7a-dihydro-2H-cyclopenta[b]pyran-6-one (2.11), flaccidoxide (2.18) and 11S,12S-epoxycembra-1Z,3E,7E-trien-14S-ol (2.19)] and a new diterpene [13S,14R-diacetoxy-11S,12R-epoxycembra-1Z,3E,7E-triene (2.20)] were isolated and identified using standard spectroscopic techniques. Anomalies in the published spectral data of 2.1 and 2.8 were exposed and corrected, and the absolute stereochemistry of the cembrane diterpenes 2.18 and 2.20 established using the modified Mosher’s method. The comparative activities of the nine natural products against four cancer cell lines (A549, LOX, OVCAR3, SNB19) are reported. The second part of the thesis (Chapter Three – Chapter Six) is concerned with an ecological, structural and synthetic study of diterpenes from the endemic South African pulmonate limpet Trimusculus costatus. Two new labdane diterpenes [6b,7a-diacetoxylabda-8,13E-dien-15-ol (3.10) and 2a,6b,7a-triacetoxylabda-8,13E-dien-15-ol (3.11)] were isolated from T. costatus and evaluated for anti-feeding activity against the common predatory fish Pomadasys commersonnii. A strategy for the semi-synthesis of 3.10 from rhinocerotinoic acid (4.14), a diterpene reportedly present in the ubiquitous South African shrub Elytropappus rhinocerotis, was devised in order to allow further bioactivity tests to be performed and unequivocally assign the unknown absolute stereochemistry of the T. costatus metabolites. Attempts to isolate rhinocerotinoic acid from local specimens of Elytropappus rhinocerotis were unsuccessful, and as the repetition of a published synthesis of 4.14 from (-)-sclareol (4.15) gave rhinocerotinoic acid in unacceptably low yields with poor stereoselectivity, an improved synthesis of 4.14 is presented. Comprehensive studies using hispanone (5.1) as a model compound showed that 6,7-dioxygenated labda-8-enes could be prepared from compounds possessing a 7-oxo-labda-8-ene skeleton with some degree of stereocontrol. In the process, fourteen new hispanone analogues were prepared and most of these were tested for activity in a suite of ten agro-chemical assays. The novel compound 7b-hydroxy-9a-carbonitrile-15,16-epoxylabda-13(16),14-dien-6-one (5.34) exhibited significant activity against the crop fungus Phytophthora infestans and is currently being subjected to further agro-chemical tests. Unfortunately, the results from the oxygenation study performed on the model compound 5.1 could not be directly extrapolated to rhinocerotinoic acid. Attempts to prepare the naturally occurring 3.10 from 4.14 via an alternative route were unsuccessful but yielded an analogue of 3.10 in which the substituents at C-6 and C-7 are in a diequatorial rather than a diaxial configuration.
- Full Text:
- Date Issued: 2003
- Authors: Gray, Christopher Anthony
- Date: 2003
- Subjects: Ethyl acetoacetate Diterpenes Limpets -- South Africa Natural products -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4349 , http://hdl.handle.net/10962/d1005014
- Description: This thesis is divided into two parts. The first part (Chapter Two) documents a bioassay guided investigation of the ethyl acetate extracts of four marine invertebrates from Mozambique (an Irciniid sponge, a Haliclona sp. sponge, an ascidian tentatively identified as Diplosoma sp., and the soft coral Cladiella kashmani). Eight known compounds [ilimaquinone (2.1), renierone (2.7), N-formyl-1,2-dihydrorenierone (2.8), 1,6-dimethyl-7-methoxy-5,8-dihydroisoquinoline-5,8-dione (2.9), mimosamycin (2.10) 7Z-allylidene-5-hydroxy-7,7a-dihydro-2H-cyclopenta[b]pyran-6-one (2.11), flaccidoxide (2.18) and 11S,12S-epoxycembra-1Z,3E,7E-trien-14S-ol (2.19)] and a new diterpene [13S,14R-diacetoxy-11S,12R-epoxycembra-1Z,3E,7E-triene (2.20)] were isolated and identified using standard spectroscopic techniques. Anomalies in the published spectral data of 2.1 and 2.8 were exposed and corrected, and the absolute stereochemistry of the cembrane diterpenes 2.18 and 2.20 established using the modified Mosher’s method. The comparative activities of the nine natural products against four cancer cell lines (A549, LOX, OVCAR3, SNB19) are reported. The second part of the thesis (Chapter Three – Chapter Six) is concerned with an ecological, structural and synthetic study of diterpenes from the endemic South African pulmonate limpet Trimusculus costatus. Two new labdane diterpenes [6b,7a-diacetoxylabda-8,13E-dien-15-ol (3.10) and 2a,6b,7a-triacetoxylabda-8,13E-dien-15-ol (3.11)] were isolated from T. costatus and evaluated for anti-feeding activity against the common predatory fish Pomadasys commersonnii. A strategy for the semi-synthesis of 3.10 from rhinocerotinoic acid (4.14), a diterpene reportedly present in the ubiquitous South African shrub Elytropappus rhinocerotis, was devised in order to allow further bioactivity tests to be performed and unequivocally assign the unknown absolute stereochemistry of the T. costatus metabolites. Attempts to isolate rhinocerotinoic acid from local specimens of Elytropappus rhinocerotis were unsuccessful, and as the repetition of a published synthesis of 4.14 from (-)-sclareol (4.15) gave rhinocerotinoic acid in unacceptably low yields with poor stereoselectivity, an improved synthesis of 4.14 is presented. Comprehensive studies using hispanone (5.1) as a model compound showed that 6,7-dioxygenated labda-8-enes could be prepared from compounds possessing a 7-oxo-labda-8-ene skeleton with some degree of stereocontrol. In the process, fourteen new hispanone analogues were prepared and most of these were tested for activity in a suite of ten agro-chemical assays. The novel compound 7b-hydroxy-9a-carbonitrile-15,16-epoxylabda-13(16),14-dien-6-one (5.34) exhibited significant activity against the crop fungus Phytophthora infestans and is currently being subjected to further agro-chemical tests. Unfortunately, the results from the oxygenation study performed on the model compound 5.1 could not be directly extrapolated to rhinocerotinoic acid. Attempts to prepare the naturally occurring 3.10 from 4.14 via an alternative route were unsuccessful but yielded an analogue of 3.10 in which the substituents at C-6 and C-7 are in a diequatorial rather than a diaxial configuration.
- Full Text:
- Date Issued: 2003
Study of titanium, tantalum and chromium catalysts for use in industrial transformations
- Authors: Tau, Prudence Lerato
- Date: 2007
- Subjects: Titanium Tantalum Phthalocyanines Electrochemistry Photochemotherapy Chromium Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4363 , http://hdl.handle.net/10962/d1005028
- Description: PART A The syntheses, spectroscopic and electrochemical characterisation of a series of titanium and tantalum phthalocyanine complexes are reported. The complexes are unsubstituted and substituted at either the peripheral or non-peripheral positions with sulphonates, aryloxy, arylthio or amino groups. The complexes mostly exhibit Qbands in the near-infrared region as well as interesting properties in different solvents. The interaction of differently sulphonated titanium and tantalum phthalocyanine complexes with methyl viologen (MV[superscript 2+]), and hence the stoichiometry and association constants are evaluated. Detailed photophysicochemical properties of the complexes were investigated and are for the first time presented with fluorescence lifetimes easily obtained from fluorescence quenching studies. The transformation of 1-hexene photocatalysed by aryloxy- and arylthio-appended complexes is also presented for the first time. The electrochemical properties of the complexes are unknown and are thus presented. Cyclic (CV) and square wave (SWV) voltammetries, chronocoulometry and spectroelectrochemistry are employed in the study of the complexes. Two oneelectron reductions and a simultaneous 4-electron reduction are observed for the unsubstituted Cl[subscript 3]TaPc. Reduction occurs first at the metal followed by ring-based processes. The tetra- and octa-substituted derivatives however exhibit peculiar electrochemical behaviour where a multi-electron transfer process occurs for complexes bearing certain substituents. For all complexes, the first two reductions are metal-based followed by ring-based processes. A comparative study of the electrocatalytic activities of the complexes towards the oxidation of nitrite is also investigated. The complexes are immobilised onto a glassy carbon electrode either by drop-dry or electropolymerisation methods. All the modified electrodes exhibit improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a twoelectron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ~ 0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed. PART B: The syntheses and electrochemical characterisation of chromium and titanium complexes for the selective trimerisation of ethylene to 1-hexene are presented. The synthesis of the chromium complex requires simple steps while tedious steps are used for the air-sensitive titanium complex. The spectroscopic interaction of the chromium complex with the co-catalyst methylaluminoxane is investigated. The complexes are characterised by electrochemical methods such as cyclic voltammetry and spectroelectrochemistry.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence Lerato
- Date: 2007
- Subjects: Titanium Tantalum Phthalocyanines Electrochemistry Photochemotherapy Chromium Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4363 , http://hdl.handle.net/10962/d1005028
- Description: PART A The syntheses, spectroscopic and electrochemical characterisation of a series of titanium and tantalum phthalocyanine complexes are reported. The complexes are unsubstituted and substituted at either the peripheral or non-peripheral positions with sulphonates, aryloxy, arylthio or amino groups. The complexes mostly exhibit Qbands in the near-infrared region as well as interesting properties in different solvents. The interaction of differently sulphonated titanium and tantalum phthalocyanine complexes with methyl viologen (MV[superscript 2+]), and hence the stoichiometry and association constants are evaluated. Detailed photophysicochemical properties of the complexes were investigated and are for the first time presented with fluorescence lifetimes easily obtained from fluorescence quenching studies. The transformation of 1-hexene photocatalysed by aryloxy- and arylthio-appended complexes is also presented for the first time. The electrochemical properties of the complexes are unknown and are thus presented. Cyclic (CV) and square wave (SWV) voltammetries, chronocoulometry and spectroelectrochemistry are employed in the study of the complexes. Two oneelectron reductions and a simultaneous 4-electron reduction are observed for the unsubstituted Cl[subscript 3]TaPc. Reduction occurs first at the metal followed by ring-based processes. The tetra- and octa-substituted derivatives however exhibit peculiar electrochemical behaviour where a multi-electron transfer process occurs for complexes bearing certain substituents. For all complexes, the first two reductions are metal-based followed by ring-based processes. A comparative study of the electrocatalytic activities of the complexes towards the oxidation of nitrite is also investigated. The complexes are immobilised onto a glassy carbon electrode either by drop-dry or electropolymerisation methods. All the modified electrodes exhibit improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a twoelectron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ~ 0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed. PART B: The syntheses and electrochemical characterisation of chromium and titanium complexes for the selective trimerisation of ethylene to 1-hexene are presented. The synthesis of the chromium complex requires simple steps while tedious steps are used for the air-sensitive titanium complex. The spectroscopic interaction of the chromium complex with the co-catalyst methylaluminoxane is investigated. The complexes are characterised by electrochemical methods such as cyclic voltammetry and spectroelectrochemistry.
- Full Text:
- Date Issued: 2007
Development of molecularly imprinted polymer based solid phase extraction sorbents for the selective cleanup of food and pharmaceutical residue samples
- Authors: Batlokwa, Bareki Shima
- Date: 2012
- Subjects: Sorbents -- Research Nanofibers -- Research Aflatoxins -- Research Electrospinning -- Research Extraction (Chemistry) -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4309 , http://hdl.handle.net/10962/d1004967
- Description: This thesis presents the development of chlorophyll, cholic acid, aflatoxin B1 molecularly imprinted polymer (MIP) particles and cholic acid MIP nanofibers for application as selective solid phase extraction (SPE) sorbents. The particles were prepared by bulk polymerization and the nanofibers by a novel approach combining molecular imprinting and electrospinning technology. The AFB1 MIP particles were compared with an aflatoxin specific immunoextraction sorbent in cleaning-up and pre-concentrating aflatoxins from nut extracts. They both recorded high extraction efficiencies (EEs) of > 97 % in selectively extracting the aflatoxins (AFB1, AFB2, AFG1 and AFG2). High reproducibility marked by the low %RSDs of < 1% and low LODs of ≤ 0.02 ng/g were calculated in all cases. The LODs were within the monitoring requirements of the European Commission. The results were validated with a peanut butter certified reference material. The chlorophyll MIP on the other hand selectively removed chlorophyll that would otherwise interfere during pesticide residue analysis (PRA) from > 0.6 to <0.09 Au in green plants extracts. The extracted chlorophyll was removed to far below the level of ≥ 0.399 Au that is usually associated with interference during PRA. Furthermore, the MIP demonstrated better selectivity by removing only chlorophyll (> 99%) in the presence of planar pesticides than the currently employed graphitized carbon black (GCB) that removed both the chlorophyll (> 88%) and planar pesticides (> 89%). For the interfering cholic acid during drug residue analysis, cholic acid MIP electrospun nanofibers demonstrated to be more sensitive and possessing higher loading capacity than the MIP particles. 100% cholic acid was removed by the nanofibers from standard solutions relative to 80% by the particles. This showed that the nanofibers have better performance than the micro particles and as such have potential to replace the particle based SPE sorbents that are currently in use. All the templates were optimally removed from the prepared MIPs by employing a novel pressurized hot water extraction template removal method that was used for the first time in this thesis. The method employed only water, an environmentally friendly solvent to remove templates to ≥ 99.6% with template residual bleeding of ≤ 0.02%.
- Full Text:
- Date Issued: 2012
- Authors: Batlokwa, Bareki Shima
- Date: 2012
- Subjects: Sorbents -- Research Nanofibers -- Research Aflatoxins -- Research Electrospinning -- Research Extraction (Chemistry) -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4309 , http://hdl.handle.net/10962/d1004967
- Description: This thesis presents the development of chlorophyll, cholic acid, aflatoxin B1 molecularly imprinted polymer (MIP) particles and cholic acid MIP nanofibers for application as selective solid phase extraction (SPE) sorbents. The particles were prepared by bulk polymerization and the nanofibers by a novel approach combining molecular imprinting and electrospinning technology. The AFB1 MIP particles were compared with an aflatoxin specific immunoextraction sorbent in cleaning-up and pre-concentrating aflatoxins from nut extracts. They both recorded high extraction efficiencies (EEs) of > 97 % in selectively extracting the aflatoxins (AFB1, AFB2, AFG1 and AFG2). High reproducibility marked by the low %RSDs of < 1% and low LODs of ≤ 0.02 ng/g were calculated in all cases. The LODs were within the monitoring requirements of the European Commission. The results were validated with a peanut butter certified reference material. The chlorophyll MIP on the other hand selectively removed chlorophyll that would otherwise interfere during pesticide residue analysis (PRA) from > 0.6 to <0.09 Au in green plants extracts. The extracted chlorophyll was removed to far below the level of ≥ 0.399 Au that is usually associated with interference during PRA. Furthermore, the MIP demonstrated better selectivity by removing only chlorophyll (> 99%) in the presence of planar pesticides than the currently employed graphitized carbon black (GCB) that removed both the chlorophyll (> 88%) and planar pesticides (> 89%). For the interfering cholic acid during drug residue analysis, cholic acid MIP electrospun nanofibers demonstrated to be more sensitive and possessing higher loading capacity than the MIP particles. 100% cholic acid was removed by the nanofibers from standard solutions relative to 80% by the particles. This showed that the nanofibers have better performance than the micro particles and as such have potential to replace the particle based SPE sorbents that are currently in use. All the templates were optimally removed from the prepared MIPs by employing a novel pressurized hot water extraction template removal method that was used for the first time in this thesis. The method employed only water, an environmentally friendly solvent to remove templates to ≥ 99.6% with template residual bleeding of ≤ 0.02%.
- Full Text:
- Date Issued: 2012