The electrocatalytic activity of metallophthalocyanines and their conjugates with carbon nanomaterials and metal tungstate nanoparticles
- Authors: Ndebele, Nobuhle
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Nitrites , Dopamine , Catechol , Detection limit
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/431934 , vital:72816 , DOI 10.21504/10962/431933
- Description: In this dissertation, seventeen phthalocyanine complexes were synthesised. Of these, only four are known and have been published. These complexes were synthesised using the conventional statistical condensation method that involves refluxing the phthalonitrile(s) (4-((1,3-bis(dimethylamino)propan-2-yl)oxy)phthalonitrile, 4-(4-carboxyphenoxy)phthalonitrile, 4-(4-acetylphenoxy)phthalonitrile, dimethyl 5-(3,4-dicyanophenoxy)-isophthalate, 4-(4-(tert-butyl)phenoxy)phthalonitrile, 5-phenoxylpicolinic acid phthalonitrile 4-(4-formylphenoxy) phthalonitrile, and 4-(4-(3-oxo-3-phenylprop-1-enyl) phenoxy) phthalonitrile) with the metal salt and 1,8-diazabicyclo[5.4.0]undecane as a catalyst in a high-temperature solvent. And thereafter (when necessary), isolation and purification of the target compounds were achieved through the use of silica column chromatography. These compounds were characterised using various analytical techniques such as; ultraviolet-visible absorption, mass spectroscopy, and Fourier transform infrared spectra and elemental analysis. These techniques proved that the complexes were successfully synthesised and isolated as pure compounds. Carbon-based (graphene quantum dots and nitrogen-doped graphene quantum dots) and metal oxide (bismuth tungsten oxide and nickel tungsten oxide) nanomaterials were synthesised. Together with the purchased single-walled carbon nanotubes, these nanomaterials were conjugated to some of the MPc complexes via non-covalent (carbon-based nanomaterials) and covalent (metal oxides) linkage forming hybrid materials. These nanomaterials and hybrids were characterised using various analytical methods (ultraviolet-visible absorption, X-ray diffraction, Raman spectroscopy, thermographic analysis, and dynamic light scattering). Nanomaterials were utilised herein to determine their effect on the properties of MPc complexes and provide a synergistic effect in the hope of enhancing these properties. All complexes synthesised in this work (MPcs, nanomaterials and hybrids) were employed as electrocatalysts in electrochemical sensing. These electrocatalysts were embedded onto the glassy carbon electrode via an adsorption method known as drop-casting. The modified electrode surfaces were characterised using cyclic voltammetry, electrochemical impedance spectroscopy and scanning electrochemical microscopy to determine various electrochemical parameters. These electrocatalysts were used in the detection of either nitrite, catechol and/or dopamine. The detection limits, sensitivities, kinetics and catalytic constants were among other parameters determined for each electrocatalyst. These electrocatalysts proved to be stable electrocatalysts that could potentially be used for practical applications. The determined parameters were comparable and sometimes better than those obtained in literature. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
- Authors: Ndebele, Nobuhle
- Date: 2023-10-13
- Subjects: Phthalocyanines , Electrocatalysis , Nitrites , Dopamine , Catechol , Detection limit
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/431934 , vital:72816 , DOI 10.21504/10962/431933
- Description: In this dissertation, seventeen phthalocyanine complexes were synthesised. Of these, only four are known and have been published. These complexes were synthesised using the conventional statistical condensation method that involves refluxing the phthalonitrile(s) (4-((1,3-bis(dimethylamino)propan-2-yl)oxy)phthalonitrile, 4-(4-carboxyphenoxy)phthalonitrile, 4-(4-acetylphenoxy)phthalonitrile, dimethyl 5-(3,4-dicyanophenoxy)-isophthalate, 4-(4-(tert-butyl)phenoxy)phthalonitrile, 5-phenoxylpicolinic acid phthalonitrile 4-(4-formylphenoxy) phthalonitrile, and 4-(4-(3-oxo-3-phenylprop-1-enyl) phenoxy) phthalonitrile) with the metal salt and 1,8-diazabicyclo[5.4.0]undecane as a catalyst in a high-temperature solvent. And thereafter (when necessary), isolation and purification of the target compounds were achieved through the use of silica column chromatography. These compounds were characterised using various analytical techniques such as; ultraviolet-visible absorption, mass spectroscopy, and Fourier transform infrared spectra and elemental analysis. These techniques proved that the complexes were successfully synthesised and isolated as pure compounds. Carbon-based (graphene quantum dots and nitrogen-doped graphene quantum dots) and metal oxide (bismuth tungsten oxide and nickel tungsten oxide) nanomaterials were synthesised. Together with the purchased single-walled carbon nanotubes, these nanomaterials were conjugated to some of the MPc complexes via non-covalent (carbon-based nanomaterials) and covalent (metal oxides) linkage forming hybrid materials. These nanomaterials and hybrids were characterised using various analytical methods (ultraviolet-visible absorption, X-ray diffraction, Raman spectroscopy, thermographic analysis, and dynamic light scattering). Nanomaterials were utilised herein to determine their effect on the properties of MPc complexes and provide a synergistic effect in the hope of enhancing these properties. All complexes synthesised in this work (MPcs, nanomaterials and hybrids) were employed as electrocatalysts in electrochemical sensing. These electrocatalysts were embedded onto the glassy carbon electrode via an adsorption method known as drop-casting. The modified electrode surfaces were characterised using cyclic voltammetry, electrochemical impedance spectroscopy and scanning electrochemical microscopy to determine various electrochemical parameters. These electrocatalysts were used in the detection of either nitrite, catechol and/or dopamine. The detection limits, sensitivities, kinetics and catalytic constants were among other parameters determined for each electrocatalyst. These electrocatalysts proved to be stable electrocatalysts that could potentially be used for practical applications. The determined parameters were comparable and sometimes better than those obtained in literature. , Thesis (PhD) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
Electrospun fibre based colorimetric probes for biological molecules
- Authors: Mudabuka, Boitumelo
- Date: 2014
- Subjects: Nanofibers , Vitamin C , Dopamine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4535 , http://hdl.handle.net/10962/d1016354
- Description: The thesis reports the use of electrospun nanofibres as a platform for the development of colorimetric probes. Three colorimetric probes in the form of electrospun nanofibre test strips were developed for the selective detection of ascorbic acid and dopamine because they are crucial biomolecules for physiological processes in human metabolism and usually coexist in biological samples. The simultaneous detection of the biomolecules is very important as their abnormal concentration levels would lead to diseases such as Parkinson's and schizophrenia. Different methods of incorporating detector agents into the nanofibre were exploited for the detection of the biomolecules. The methods included physical incorporation of nanoparticles, covalent bonding of ligand/dyes through surface modification of the fibres. The first colorimetric test strip for ascorbic acid was based on copper-gold alloy nanoparticles prepared in-situ and hosted in nylon6. The test strip showed selectivity in detecting ascorbic acid in the pH range 2 – 7. The suitability of fibres in hosting copper-gold alloy nanoparticles for the colorimetric detection of ascorbic acid was investigated using nylon6, poly(vinyl benzyl chloride)-styrene and cellulose acetate based test strips. All the test strips exhibited leaching and the nylon6 based test strip was found to be thermally stable up to 60 ˚C. The colorimetric performance of the test strips was maintained and neither was colour decay exhibited after 10 months of storage in a shelf. The test strip achieved an eye-ball limit of detection of 1.76 x10-2 mg L-1 and its suitability was demonstrated by the determination of ascorbic acid in fruit juices, urine, serum, and vitamin C tablets. The second colorimetric test strip for ascorbic acid and dopamine employed prussian blue synthesised in-situ in nylon6. Ascorbic acid turned the deep blue test strip to light blue at pH 3, and a faded navy blue colour at a pH range of 6 - 7 while dopamine changed the strip to purple at the same pH range. The versatility of the test strip was demonstrated by detecting ascorbic acid in commercial fruit juices as well as by detecting ascorbic acid as well as dopamine in fortified urine. The eye-ball detection limit of the Prussian blue test strip for ascorbic acid and dopamine was 17.6 mg L-1 and 18.9 mg L-1, respectively. The third method involved a covalent approach, where poly(vinylbenzyl chloride) nanofibers were post functionalised with 2-(2′-pyridyl)-imidazole and iron(III) for the selective detection of ascorbic acid and dopamine. The eye-ball detection limit for ascorbic acid and dopamine was 17.6 mg L-1 and 18.9 mg L-1, respectively. The test strip was selective for dopamine, but the detection of ascorbic acid suffered from interference by glutathione. The application of the test strips was nevertheless demonstrated by the detection of ascorbic acid in fruit juices and dopamine in fortified urine. The developed test strips employing the three approaches were applied without sample pre-treatment and use of supporting equipment.
- Full Text:
- Date Issued: 2014
- Authors: Mudabuka, Boitumelo
- Date: 2014
- Subjects: Nanofibers , Vitamin C , Dopamine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4535 , http://hdl.handle.net/10962/d1016354
- Description: The thesis reports the use of electrospun nanofibres as a platform for the development of colorimetric probes. Three colorimetric probes in the form of electrospun nanofibre test strips were developed for the selective detection of ascorbic acid and dopamine because they are crucial biomolecules for physiological processes in human metabolism and usually coexist in biological samples. The simultaneous detection of the biomolecules is very important as their abnormal concentration levels would lead to diseases such as Parkinson's and schizophrenia. Different methods of incorporating detector agents into the nanofibre were exploited for the detection of the biomolecules. The methods included physical incorporation of nanoparticles, covalent bonding of ligand/dyes through surface modification of the fibres. The first colorimetric test strip for ascorbic acid was based on copper-gold alloy nanoparticles prepared in-situ and hosted in nylon6. The test strip showed selectivity in detecting ascorbic acid in the pH range 2 – 7. The suitability of fibres in hosting copper-gold alloy nanoparticles for the colorimetric detection of ascorbic acid was investigated using nylon6, poly(vinyl benzyl chloride)-styrene and cellulose acetate based test strips. All the test strips exhibited leaching and the nylon6 based test strip was found to be thermally stable up to 60 ˚C. The colorimetric performance of the test strips was maintained and neither was colour decay exhibited after 10 months of storage in a shelf. The test strip achieved an eye-ball limit of detection of 1.76 x10-2 mg L-1 and its suitability was demonstrated by the determination of ascorbic acid in fruit juices, urine, serum, and vitamin C tablets. The second colorimetric test strip for ascorbic acid and dopamine employed prussian blue synthesised in-situ in nylon6. Ascorbic acid turned the deep blue test strip to light blue at pH 3, and a faded navy blue colour at a pH range of 6 - 7 while dopamine changed the strip to purple at the same pH range. The versatility of the test strip was demonstrated by detecting ascorbic acid in commercial fruit juices as well as by detecting ascorbic acid as well as dopamine in fortified urine. The eye-ball detection limit of the Prussian blue test strip for ascorbic acid and dopamine was 17.6 mg L-1 and 18.9 mg L-1, respectively. The third method involved a covalent approach, where poly(vinylbenzyl chloride) nanofibers were post functionalised with 2-(2′-pyridyl)-imidazole and iron(III) for the selective detection of ascorbic acid and dopamine. The eye-ball detection limit for ascorbic acid and dopamine was 17.6 mg L-1 and 18.9 mg L-1, respectively. The test strip was selective for dopamine, but the detection of ascorbic acid suffered from interference by glutathione. The application of the test strips was nevertheless demonstrated by the detection of ascorbic acid in fruit juices and dopamine in fortified urine. The developed test strips employing the three approaches were applied without sample pre-treatment and use of supporting equipment.
- Full Text:
- Date Issued: 2014
An investigation into the neuroprotective and neurotoxic properties of levodopa, dopamine and selegiline
- Authors: Scheepers, Mark Wesley
- Date: 2008
- Subjects: Parkinson's disease , Nervous system -- Degeneration -- Treatment , Neurotoxic agents , Neuroanatomy , Oxidative stress , Pharmacology , Dopamine , Selegiline , Dopaminergic neurons
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3789 , http://hdl.handle.net/10962/d1003267 , Parkinson's disease , Nervous system -- Degeneration -- Treatment , Neurotoxic agents , Neuroanatomy , Oxidative stress , Pharmacology , Dopamine , Selegiline , Dopaminergic neurons
- Description: Parkinson’s disease (PD) is a neurodegenerative disorder characterized by a profound loss of dopaminergic neurons from the substantia nigra (SN). Among the many pathogenic mechanisms thought to be responsible for the demise of these cells, dopamine (DA)-dependent oxidative stress and oxidative damage has taken center stage due to extensive experimental evidence showing that DA-derived reactive oxygen species (ROS) and oxidized DA metabolites are toxic to SN neurons. Despite its being the most efficacious drug for symptom reversal in PD, there is concern that levodopa (LD) may contribute to the neuronal degeneration and progression of PD by enhancing DA concentrations and turnover in surviving dopaminergic neurons. The present study investigates the potential neurotoxic and neuroprotective effects of DA in vitro. These effects are compared to the toxicity and neuroprotective effects observed in the rat striatum after the administration of LD and selegiline (SEL), both of which increase striatal DA levels. The effects of exogenous LD and/or SEL administration on both the oxidative stress caused by increased striatal iron (II) levels and its consequences have also been investigated. 6-Hydroxydopamine (6-OHDA) is a potent neurotoxin used to mimic dopaminergic degeneration in animal models of PD. The formation of 6-OHDA in vivo could destroy central dopaminergic nerve terminals and enhance the progression of PD. Inorganic studies using high performance liquid chromatography with electrochemical detection (HPLC-ECD) show that hydroxyl radicals can react with DA to form 6-OHDA in vitro. SEL results in a significant decrease in the formation of 6-OHDA in vitro, probably as a result of its antioxidant properties. However, the exogenous administration of LD, with or without SEL, either does not lead to the formation of striatal 6-OHDA in vivo or produces concentrations below the detection limit of the assay. This is despite the fact that striatal DA levels in these rats are significantly elevated (two-fold) compared to the control group. The auto-oxidation and monoamine oxidase (MAO)-mediated metabolism of DA causes an increase in the production of superoxide anions in whole rat brain homogenate in vitro. In addition to this, DA is able to enhance the production of hydroxyl radicals by Fenton chemistry (Fe(III)-EDTA/H2O2) in a cell free environment. Treatment with systemic LD elevates the production of striatal superoxide anions, but does not lead to a detectable increase in striatal hydroxyl radical production in vivo. The co-adminstration of SEL with LD is able to prevent the LD induced rise in striatal superoxide levels. It has been found that the presence of DA or 6-OHDA is able to reduce lipid peroxidation in whole rat brain homogenate induced by Fe(II)-EDTA/H2O2 and ascorbate (Fenton system). However, DA and 6-OHDA increase protein oxidation in rat brain homogenate, which is further increased in the presence of the Fenton system. In addition to this, the incubation of rat brain homogenate with DA or 6-OHDA is also accompanied by a significant reduction in the total GSH content of the homogenate. The exogenous administration of LD and/or SEL was found to have no detrimental effects on striatal lipids, proteins or total GSH levels. Systemic LD administration actually had a neuroprotective effect in the striatum by inhibiting iron (II) induced lipid peroxidation. Inorganic studies, including electrochemistry and the ferrozine assay show that DA and 6-OHDA are able to release iron from ferritin, as iron (II), and that DA can bind iron (III), a fact that may easily impede the availability of this metal ion for participation in the Fenton reaction. The binding of iron (III) by DA appears to discard the involvement of the Fenton reaction in the increased production of hydroxyl radicals induced by the addition of DA to mixtures containing Fe(II)-EDTA and hydrogen peroxide. 6-OHDA did not form a metal-ligand complex with iron (II) or iron (III). In addition to the antioxidant activity and MAO-B inhibitory activity of SEL, the iron binding studies show that SEL has weak iron (II) chelating activity and that it can also form complexes with iron (III). This may therefore be another mechanism involved in the neuroprotective action of SEL. The results of the pineal indole metabolism study show that the systemic administration of SEL increases the production of N-acetylserotonin (NAS) by the pineal gland. NAS has been demonstrated to be a potent antioxidant in the brain and protects against 6-OHDA induced toxicity. The results of this study show that DA displays antioxidant properties in relation to lipid eroxidation and exhibits pro-oxidant properties by causing an increase in the production of hydroxyl radicals and superoxide anions, as well as protein oxidation and a loss of total GSH content. Despite the toxic effects of DA in vitro, the treatment of rats with exogenous LD does not cause oxidative stress or oxidative damage. The results also show that LD and SEL have some neuroprotective properties which make these agents useful in the treatment of PD.
- Full Text:
- Date Issued: 2008
- Authors: Scheepers, Mark Wesley
- Date: 2008
- Subjects: Parkinson's disease , Nervous system -- Degeneration -- Treatment , Neurotoxic agents , Neuroanatomy , Oxidative stress , Pharmacology , Dopamine , Selegiline , Dopaminergic neurons
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3789 , http://hdl.handle.net/10962/d1003267 , Parkinson's disease , Nervous system -- Degeneration -- Treatment , Neurotoxic agents , Neuroanatomy , Oxidative stress , Pharmacology , Dopamine , Selegiline , Dopaminergic neurons
- Description: Parkinson’s disease (PD) is a neurodegenerative disorder characterized by a profound loss of dopaminergic neurons from the substantia nigra (SN). Among the many pathogenic mechanisms thought to be responsible for the demise of these cells, dopamine (DA)-dependent oxidative stress and oxidative damage has taken center stage due to extensive experimental evidence showing that DA-derived reactive oxygen species (ROS) and oxidized DA metabolites are toxic to SN neurons. Despite its being the most efficacious drug for symptom reversal in PD, there is concern that levodopa (LD) may contribute to the neuronal degeneration and progression of PD by enhancing DA concentrations and turnover in surviving dopaminergic neurons. The present study investigates the potential neurotoxic and neuroprotective effects of DA in vitro. These effects are compared to the toxicity and neuroprotective effects observed in the rat striatum after the administration of LD and selegiline (SEL), both of which increase striatal DA levels. The effects of exogenous LD and/or SEL administration on both the oxidative stress caused by increased striatal iron (II) levels and its consequences have also been investigated. 6-Hydroxydopamine (6-OHDA) is a potent neurotoxin used to mimic dopaminergic degeneration in animal models of PD. The formation of 6-OHDA in vivo could destroy central dopaminergic nerve terminals and enhance the progression of PD. Inorganic studies using high performance liquid chromatography with electrochemical detection (HPLC-ECD) show that hydroxyl radicals can react with DA to form 6-OHDA in vitro. SEL results in a significant decrease in the formation of 6-OHDA in vitro, probably as a result of its antioxidant properties. However, the exogenous administration of LD, with or without SEL, either does not lead to the formation of striatal 6-OHDA in vivo or produces concentrations below the detection limit of the assay. This is despite the fact that striatal DA levels in these rats are significantly elevated (two-fold) compared to the control group. The auto-oxidation and monoamine oxidase (MAO)-mediated metabolism of DA causes an increase in the production of superoxide anions in whole rat brain homogenate in vitro. In addition to this, DA is able to enhance the production of hydroxyl radicals by Fenton chemistry (Fe(III)-EDTA/H2O2) in a cell free environment. Treatment with systemic LD elevates the production of striatal superoxide anions, but does not lead to a detectable increase in striatal hydroxyl radical production in vivo. The co-adminstration of SEL with LD is able to prevent the LD induced rise in striatal superoxide levels. It has been found that the presence of DA or 6-OHDA is able to reduce lipid peroxidation in whole rat brain homogenate induced by Fe(II)-EDTA/H2O2 and ascorbate (Fenton system). However, DA and 6-OHDA increase protein oxidation in rat brain homogenate, which is further increased in the presence of the Fenton system. In addition to this, the incubation of rat brain homogenate with DA or 6-OHDA is also accompanied by a significant reduction in the total GSH content of the homogenate. The exogenous administration of LD and/or SEL was found to have no detrimental effects on striatal lipids, proteins or total GSH levels. Systemic LD administration actually had a neuroprotective effect in the striatum by inhibiting iron (II) induced lipid peroxidation. Inorganic studies, including electrochemistry and the ferrozine assay show that DA and 6-OHDA are able to release iron from ferritin, as iron (II), and that DA can bind iron (III), a fact that may easily impede the availability of this metal ion for participation in the Fenton reaction. The binding of iron (III) by DA appears to discard the involvement of the Fenton reaction in the increased production of hydroxyl radicals induced by the addition of DA to mixtures containing Fe(II)-EDTA and hydrogen peroxide. 6-OHDA did not form a metal-ligand complex with iron (II) or iron (III). In addition to the antioxidant activity and MAO-B inhibitory activity of SEL, the iron binding studies show that SEL has weak iron (II) chelating activity and that it can also form complexes with iron (III). This may therefore be another mechanism involved in the neuroprotective action of SEL. The results of the pineal indole metabolism study show that the systemic administration of SEL increases the production of N-acetylserotonin (NAS) by the pineal gland. NAS has been demonstrated to be a potent antioxidant in the brain and protects against 6-OHDA induced toxicity. The results of this study show that DA displays antioxidant properties in relation to lipid eroxidation and exhibits pro-oxidant properties by causing an increase in the production of hydroxyl radicals and superoxide anions, as well as protein oxidation and a loss of total GSH content. Despite the toxic effects of DA in vitro, the treatment of rats with exogenous LD does not cause oxidative stress or oxidative damage. The results also show that LD and SEL have some neuroprotective properties which make these agents useful in the treatment of PD.
- Full Text:
- Date Issued: 2008
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