Electrochemical studies of gold bioaccumulation by yeast cell wall components
- Authors: Lack, Barbara Anne
- Date: 1999
- Subjects: Hydrometallurgy , Electrochemical analysis , Gold ores , Gold
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4311 , http://hdl.handle.net/10962/d1004969 , Hydrometallurgy , Electrochemical analysis , Gold ores , Gold
- Description: Gold, amongst other group 11 metals, was almost certainly one of the first three metals known to man. In addition to the economic importance of the metal, gold has a wide variety of applications in the medical, electrocatalytical and micro-electronics fields. However, the determination of gold ions in solution, with accuracy, precision, sensitivity and selectivity is still an interesting and much debated topic in analytical chemistry. A system whereby gold ions have been successfully detected employing an electrochemical technique, known as stripping voltammetry, has been developed. The electrochemical method was chosen over other available techniques for the sensitivity, particularly at low concentrations, and selectivity properties; notably in the presence of other metal ions. Under acidic conditions, the electrochemical technique was applied and the presence of gold(III), at a concentration of 2.53 x 10⁻⁵ mol dm⁻³ in a mine waste water sample, was detected. Biomass, in particular yeast and algal types, have been successfully employed in extracting low concentrations of gold ions from industrial effluents. The manipulation of the biological facility for mineral interaction, biohydrometallurgy, may yield numerous potential new technologies. South Africa in particular would benefit from this area of research, since the country is a major ore and metal refining country and if the output and the efficiency of the mines could be improved, even by a small percentage, the financial rewards would be vast. In this study, the application of adsorptive cathodic stripping voltammetry (AdCSV) of gold(III) in the presence of various Saccharomyces cerevisiae cell wall components, was investigated to determine which, if any, were involved specifically in the chemical binding of the gold ions. The chitin and mannan extracts showed the most promise with detection limits of 1.10 x 10⁻⁶ mol dm⁻³ and 9 x 10⁻⁹ mol dm⁻³, respectively; employing the AdCSV technique. A modification of the stripping voltammetry technique, Osteryoung square wave stripping voltammetry (OSWSV), provided the lowest detection limit, for gold(IIl) in the presence of mannan, of 1.70 x 10⁻¹¹ mol dm⁻³ ; utilising a modified carbon paste electrode. The detection of gold(III) has been shown to be dependent on the type of electrode employed, the electrolyte solution and the presence of interfering agents. The effect of copper(II) and silver(I) on the detection of the gold(III) in solution was investigated; whilst the silver(I) has shown no detrimental effects on gold (III) detection systems, copper(II) has indicated the possibility of forming an inter-metallic compound with the gold(III). However, mannan has shown to selectively and preferentially bind the gold(III) in the presence of a ten-fold excess of copper(II). Nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, as well as computer modelling techniques were employed to further investIgate the mannan-gold(III) interaction and proposed complex formed. The NMR, IR and computer modelling data are in agreement with the electrochemical data on proposing a mannan-gold(III) complex. The co-ordination site was established to be in the vicinity of the H-I and H-2 protons and the gold(III) adopts a square-planar geometry upon co-ordination. The benefits of the research are useful from a biological perspective (i. e. as more is known about the binding sites, microbiologists/biochemists may work on the optimisation of parameters for these sites or work could be furthered into the enhanced expression of the sites) and an industrial one. In addition to the' two major benefits, an improved understanding of gold and its chemistry would be achieved, which is advantageous for other fields of research as well.
- Full Text:
- Authors: Lack, Barbara Anne
- Date: 1999
- Subjects: Hydrometallurgy , Electrochemical analysis , Gold ores , Gold
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4311 , http://hdl.handle.net/10962/d1004969 , Hydrometallurgy , Electrochemical analysis , Gold ores , Gold
- Description: Gold, amongst other group 11 metals, was almost certainly one of the first three metals known to man. In addition to the economic importance of the metal, gold has a wide variety of applications in the medical, electrocatalytical and micro-electronics fields. However, the determination of gold ions in solution, with accuracy, precision, sensitivity and selectivity is still an interesting and much debated topic in analytical chemistry. A system whereby gold ions have been successfully detected employing an electrochemical technique, known as stripping voltammetry, has been developed. The electrochemical method was chosen over other available techniques for the sensitivity, particularly at low concentrations, and selectivity properties; notably in the presence of other metal ions. Under acidic conditions, the electrochemical technique was applied and the presence of gold(III), at a concentration of 2.53 x 10⁻⁵ mol dm⁻³ in a mine waste water sample, was detected. Biomass, in particular yeast and algal types, have been successfully employed in extracting low concentrations of gold ions from industrial effluents. The manipulation of the biological facility for mineral interaction, biohydrometallurgy, may yield numerous potential new technologies. South Africa in particular would benefit from this area of research, since the country is a major ore and metal refining country and if the output and the efficiency of the mines could be improved, even by a small percentage, the financial rewards would be vast. In this study, the application of adsorptive cathodic stripping voltammetry (AdCSV) of gold(III) in the presence of various Saccharomyces cerevisiae cell wall components, was investigated to determine which, if any, were involved specifically in the chemical binding of the gold ions. The chitin and mannan extracts showed the most promise with detection limits of 1.10 x 10⁻⁶ mol dm⁻³ and 9 x 10⁻⁹ mol dm⁻³, respectively; employing the AdCSV technique. A modification of the stripping voltammetry technique, Osteryoung square wave stripping voltammetry (OSWSV), provided the lowest detection limit, for gold(IIl) in the presence of mannan, of 1.70 x 10⁻¹¹ mol dm⁻³ ; utilising a modified carbon paste electrode. The detection of gold(III) has been shown to be dependent on the type of electrode employed, the electrolyte solution and the presence of interfering agents. The effect of copper(II) and silver(I) on the detection of the gold(III) in solution was investigated; whilst the silver(I) has shown no detrimental effects on gold (III) detection systems, copper(II) has indicated the possibility of forming an inter-metallic compound with the gold(III). However, mannan has shown to selectively and preferentially bind the gold(III) in the presence of a ten-fold excess of copper(II). Nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, as well as computer modelling techniques were employed to further investIgate the mannan-gold(III) interaction and proposed complex formed. The NMR, IR and computer modelling data are in agreement with the electrochemical data on proposing a mannan-gold(III) complex. The co-ordination site was established to be in the vicinity of the H-I and H-2 protons and the gold(III) adopts a square-planar geometry upon co-ordination. The benefits of the research are useful from a biological perspective (i. e. as more is known about the binding sites, microbiologists/biochemists may work on the optimisation of parameters for these sites or work could be furthered into the enhanced expression of the sites) and an industrial one. In addition to the' two major benefits, an improved understanding of gold and its chemistry would be achieved, which is advantageous for other fields of research as well.
- Full Text:
Electrochemical studies of metal-ligand interactions and of metal binding proteins
- Authors: Limson, Janice Leigh
- Date: 1999
- Subjects: Electrochemical analysis , Metals -- Analysis , Proteins -- Analysis , Electrochemistry -- Technique
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4551 , http://hdl.handle.net/10962/d1018239
- Description: Electrochemical methods were researched for the analysis of metals, proteins and the identification of metal binding proteins. Adsorptive cathodic stripping voltamrnetry for metal analysis combines the inherent sensitivity of electrochemical techniques with the specificity of ligands for the nonfaradaic preconcentration of analytes at the electrode. The utility of catechol, resorcinol, 4-methylcatechol and 4-t-butylcatechol as ligands was explored for the sensitive analysis of copper, bismuth, cadmium and lead on a mercury film glassy carbon electrode. Metal complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed the highest current responses with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper. The electroanalysis of cysteine and cysteine containing proteins at carbon electrodes are impaired by slow electron transfer rates at carbon electrodes, exhibiting high overpotentials, greater than 1 V vs Ag! Agel. Metallophthalocyanines have been shown to promote the electrocatalysis of cysteine at lowered potentials. Chemical modification of electrodes with appropriate modifiers is a means of incorporating specificity into electroanalysis, with applications in electrocatalysis. A glassy carbon electrode was modified by electrodeposition of cobalt (II) tetrasulphophthalocyanine [Co(II)TSPct to produce a chemically modified glassy carbon electrode (CMGCE). The CoTSPc-CMGCE catalysed the oxidation of cysteine in the pH range 1 to 10. The significance of this electrode is an application for analysis of proteins at biological pH's. A biscyanoruthenium(II) phthalocyanine CMGCE catalysed the oxidation of cysteine at 0.43 V vs Ag/AgCl a significant lowering in the overpotential for the oxidation of cysteine. Metallothionein, a metal binding protein, is believed to be involved in metal homeostasis and detoxification in the peripheral organs of living systems. A method for the quantitative determination of this protein utilising its high cysteine content was presented. At pH 8.4 Tris-HCl buffer, and using a CoTSPc-CMGCE modified by electrodeposition of the modifier, the anodic peaks for the oxidation of metallothionein was observed at 0. 90 V vs Ag/ AgCI. Ferredoxin is a simple iron-sulphur protein. One tenth of its residues are cysteine. Ferredoxin is involved in simple electron transfer processes during photosynthesis and respiration. Electrochemical studies of spinach ferredoxin were conducted at a CoTSPc-CMGCE. Anodic currents for the oxidation of the cysteine fragment of ferredoxin was observed at 0.85 V vs Ag/AgCl in HEPES buffer at pH 7.4, representing a new method for analysis of this protein. Voltammetric studies of its ferric/ferrous transition have shown quasi-reversible waves atE~ -0.62 V vs Ag/AgCl only in the presence of promoters. At a CoTSPc-CMGCE, a cathodic wave attributed to the reduction of Fe(III)/Fe(II) was observed at Epc -0.34 V vs Ag/AgCl. This represents an alternative method for voltammetric studies of the ferric/ferrous transition at significantly lowered potentials. Melatonin, a pineal gland hormone functions m setting and entraining circadian rhythms and in neuroprotection as a free radical scavenger and general antioxidant. Using adsorptive cathodic stripping voltammetry, the binding affinities of melatonin, serotonin and tryptophan for metals, were measured. The results showed that the following metal complexes were formed: aluminium with melatonin, serotonin and tryptophan; cadmium with melatonin and tryptophan; copper with melatonin and serotonin; iron (III) with melatonin and serotonin; lead with melatonin, tryptophan and serotonin, zinc with melatonin and tryptophan and iron (II) with tryptophan. The studies suggest a further role for melatonin in the reduction of free radical generation and in metal detoxification and may explain the accumulation of aluminium in Alzheimer's disease.
- Full Text:
- Authors: Limson, Janice Leigh
- Date: 1999
- Subjects: Electrochemical analysis , Metals -- Analysis , Proteins -- Analysis , Electrochemistry -- Technique
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4551 , http://hdl.handle.net/10962/d1018239
- Description: Electrochemical methods were researched for the analysis of metals, proteins and the identification of metal binding proteins. Adsorptive cathodic stripping voltamrnetry for metal analysis combines the inherent sensitivity of electrochemical techniques with the specificity of ligands for the nonfaradaic preconcentration of analytes at the electrode. The utility of catechol, resorcinol, 4-methylcatechol and 4-t-butylcatechol as ligands was explored for the sensitive analysis of copper, bismuth, cadmium and lead on a mercury film glassy carbon electrode. Metal complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed the highest current responses with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper. The electroanalysis of cysteine and cysteine containing proteins at carbon electrodes are impaired by slow electron transfer rates at carbon electrodes, exhibiting high overpotentials, greater than 1 V vs Ag! Agel. Metallophthalocyanines have been shown to promote the electrocatalysis of cysteine at lowered potentials. Chemical modification of electrodes with appropriate modifiers is a means of incorporating specificity into electroanalysis, with applications in electrocatalysis. A glassy carbon electrode was modified by electrodeposition of cobalt (II) tetrasulphophthalocyanine [Co(II)TSPct to produce a chemically modified glassy carbon electrode (CMGCE). The CoTSPc-CMGCE catalysed the oxidation of cysteine in the pH range 1 to 10. The significance of this electrode is an application for analysis of proteins at biological pH's. A biscyanoruthenium(II) phthalocyanine CMGCE catalysed the oxidation of cysteine at 0.43 V vs Ag/AgCl a significant lowering in the overpotential for the oxidation of cysteine. Metallothionein, a metal binding protein, is believed to be involved in metal homeostasis and detoxification in the peripheral organs of living systems. A method for the quantitative determination of this protein utilising its high cysteine content was presented. At pH 8.4 Tris-HCl buffer, and using a CoTSPc-CMGCE modified by electrodeposition of the modifier, the anodic peaks for the oxidation of metallothionein was observed at 0. 90 V vs Ag/ AgCI. Ferredoxin is a simple iron-sulphur protein. One tenth of its residues are cysteine. Ferredoxin is involved in simple electron transfer processes during photosynthesis and respiration. Electrochemical studies of spinach ferredoxin were conducted at a CoTSPc-CMGCE. Anodic currents for the oxidation of the cysteine fragment of ferredoxin was observed at 0.85 V vs Ag/AgCl in HEPES buffer at pH 7.4, representing a new method for analysis of this protein. Voltammetric studies of its ferric/ferrous transition have shown quasi-reversible waves atE~ -0.62 V vs Ag/AgCl only in the presence of promoters. At a CoTSPc-CMGCE, a cathodic wave attributed to the reduction of Fe(III)/Fe(II) was observed at Epc -0.34 V vs Ag/AgCl. This represents an alternative method for voltammetric studies of the ferric/ferrous transition at significantly lowered potentials. Melatonin, a pineal gland hormone functions m setting and entraining circadian rhythms and in neuroprotection as a free radical scavenger and general antioxidant. Using adsorptive cathodic stripping voltammetry, the binding affinities of melatonin, serotonin and tryptophan for metals, were measured. The results showed that the following metal complexes were formed: aluminium with melatonin, serotonin and tryptophan; cadmium with melatonin and tryptophan; copper with melatonin and serotonin; iron (III) with melatonin and serotonin; lead with melatonin, tryptophan and serotonin, zinc with melatonin and tryptophan and iron (II) with tryptophan. The studies suggest a further role for melatonin in the reduction of free radical generation and in metal detoxification and may explain the accumulation of aluminium in Alzheimer's disease.
- Full Text:
Evaluation and application of electroanalysis for the determination of antioxidants
- Authors: Ragubeer, Nasheen
- Date: 2007
- Subjects: Antioxidants , Nervous system -- Degeneration , Electrochemical analysis , Marine algae , Natural products , Marine metabolites , Sargassum , Legumes , Nuclear magnetic resonance
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3922 , http://hdl.handle.net/10962/d1003981 , Antioxidants , Nervous system -- Degeneration , Electrochemical analysis , Marine algae , Natural products , Marine metabolites , Sargassum , Legumes , Nuclear magnetic resonance
- Description: The role of antioxidants in the prevention of neurodegenerative diseases has been well documented. The use of synthetic antioxidants has decreased due to the ssociation of these compounds with certain cancers. Thus, the search for novel natural antioxidants has gained much focus in research. Most common methods of determining antioxidant capacity are the radical generated assays and biological assays such as lipid peroxidation and the nitroblue tetrazolium assay. Electrochemical methods have been proposed for the determination of bio-active compounds such as antioxidants. The electrochemical methods of cyclic voltammetry and square wave voltammetry were evaluated for the determination of antioxidant capacity initially examining known antioxidants and then using plant extracts of Sutherlandia frutescens as a case study. The antioxidant properties determined by electrochemical methods were validated utilising the non-biological methods of the DPPH, TEAC, ferrozine and FC assay and biological pharmacological methods. The results indicated that Sutherlandia frutescens contains potent antioxidant compounds that are able to reduce lipid peroxidation. The electrochemical techniques of square wave voltammetry and cyclic voltammetry were applied for the screening of a large number of extracts of various algae for the detection of antioxidant compounds. The results indicated that electrochemistry can be used as a preliminary method for the rapid screening of a large number of crude samples for antioxidant compounds. Electrochemical methods were also evaluated as a method for guiding the isolation and purification of antioxidant metabolites in Sargassum elegans. Solvent partitioning and fractionation of the marine alga allowed for the purification of antioxidant compounds. At each step of purification electrochemical methods were utilized to determine which fractions contained the more potent antioxidant compounds and thus guide further purification. The purified antioxidant compounds were elucidated using NMR to determine the structure of the antioxidant compounds.
- Full Text:
- Authors: Ragubeer, Nasheen
- Date: 2007
- Subjects: Antioxidants , Nervous system -- Degeneration , Electrochemical analysis , Marine algae , Natural products , Marine metabolites , Sargassum , Legumes , Nuclear magnetic resonance
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:3922 , http://hdl.handle.net/10962/d1003981 , Antioxidants , Nervous system -- Degeneration , Electrochemical analysis , Marine algae , Natural products , Marine metabolites , Sargassum , Legumes , Nuclear magnetic resonance
- Description: The role of antioxidants in the prevention of neurodegenerative diseases has been well documented. The use of synthetic antioxidants has decreased due to the ssociation of these compounds with certain cancers. Thus, the search for novel natural antioxidants has gained much focus in research. Most common methods of determining antioxidant capacity are the radical generated assays and biological assays such as lipid peroxidation and the nitroblue tetrazolium assay. Electrochemical methods have been proposed for the determination of bio-active compounds such as antioxidants. The electrochemical methods of cyclic voltammetry and square wave voltammetry were evaluated for the determination of antioxidant capacity initially examining known antioxidants and then using plant extracts of Sutherlandia frutescens as a case study. The antioxidant properties determined by electrochemical methods were validated utilising the non-biological methods of the DPPH, TEAC, ferrozine and FC assay and biological pharmacological methods. The results indicated that Sutherlandia frutescens contains potent antioxidant compounds that are able to reduce lipid peroxidation. The electrochemical techniques of square wave voltammetry and cyclic voltammetry were applied for the screening of a large number of extracts of various algae for the detection of antioxidant compounds. The results indicated that electrochemistry can be used as a preliminary method for the rapid screening of a large number of crude samples for antioxidant compounds. Electrochemical methods were also evaluated as a method for guiding the isolation and purification of antioxidant metabolites in Sargassum elegans. Solvent partitioning and fractionation of the marine alga allowed for the purification of antioxidant compounds. At each step of purification electrochemical methods were utilized to determine which fractions contained the more potent antioxidant compounds and thus guide further purification. The purified antioxidant compounds were elucidated using NMR to determine the structure of the antioxidant compounds.
- Full Text:
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