Catalytic reactions of platinum group metal phthalocyanines
- Authors: Sekota, Mantoa Makoena C
- Date: 1999
- Subjects: Phthalocyanines Platinum group
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4396 , http://hdl.handle.net/10962/d1006151
- Description: The voltammetric behaviour of I-cysteine and other organic compounds such as hydrazine, hydroxylamine and methionine has been studied on GCE modified with phthalocyanine complexes of osmium, rhodium and ruthenium. For cysteine oxidation, the catalytic activity of the electrode was dependent the nature of the axial ligand. When cyanide and dimethylsulphoxide (DMSO) were used as axial ligands, giving (DMSO)(Cl)Rh(III)Pc, [(CN)₂Rh(III)Pc], (DMSO)₂0S(II)Pc and [(DMSO)₂Ru(II)Pc].2DMSO complexes, the peak current increased with repetitive scanning, indicating the increase in catalytic activity of the electrode after each scan. This behaviour was not observed when pyridine was used as axial ligand. The improvement of the catalytic activity of the GCE after the first scan has been attributed to the formation of the dimeric π-cation radical species at the electrode surface. Water soluble phthalocyanine complex ([(CN)₂Os(II)Pc]²⁻) and the tetramethyltetra-pyridinoporphyrazine complexes of Pd(II) and Pt(II), ([Pd(II)2,3Tmtppa(-2)]⁴⁺, [Pd(II)3,4Tmtppa(-2)]⁴⁺, [Pt(II)2,3Tmtppa(-2)]⁴⁺ and [Pt(II)3,4Tmtppa(-2)⁴⁺) have been prepared. [(CN)₂Os(II)Pc]²⁻ is soluble in water at pH greater 4 without the formation of dimers. The [M(II)Tmtppa(-2)]⁴⁺ (M = Pd or Pt) show high solubility in water and are stable only in acidic pHs. The cyclic voltammetry of the MPc and [M(II)Tmtppa(-2)]⁴⁺ complexes prepared, is also reported. The interactions of amino acids I-histidine and I-cysteine with the [M(II)Tmtppa(-2)]⁴⁺ complexes of Pd(II) and Pt(ll) were studied. All the [M(Il)Tmtppa(-2)]⁴⁺ are readily reduced to the monoanion species [M(Il)Tmtppa(-3)]³⁻ in the presence of histidine and cysteine. The rate constants for the interaction of [M(Il)Tmtppa(-2)]⁴⁺ complexes ofPt(II) and Pd(II), with histidine and cysteine range from approximately 2 x 10⁻³ to 0.26 dm³ mol⁻¹ s⁻¹. Kinetics of the interaction of [Co(Il)TSPc]⁴⁻ with amino acids, histidine and cysteine in pH 7.2 buffer were studied. The rate constants were found to be first order in both [Co(II)TSPc]⁴⁻ and the amino acid. The formation of [Co(III)TSPc]³⁻ in the presence of histidine occurred with the rate constant of 0.16 dm³ mol⁻¹ s⁻¹, whereas the formation of the [Co(I)TSPc]⁵⁻ species in the presence of cysteine gave the rate constant of 2.2 dm³ mo⁻¹ s¹. The relative quantum yield (QΔ) for singlet oxygen production by [(CN)₂Os(Il)Pc]²⁻, and [(CN)⁴Ru(II)Pc]²⁻ in DMF using diphenylisobenzofuran (DPBF) and a chemical quencher were determined. The quantum yield values were obtained as 0.39 ± 0.05 , and 0.76 ± 0.02 for [(CN₂Os(II)Pc]²⁻ and [(CN)₂Ru(II)Pc]²⁻ respectively. The differences in quantum yield values have been explained in terms of donor abilities of both the central metal and the axial ligands.
- Full Text:
- Date Issued: 1999
- Authors: Sekota, Mantoa Makoena C
- Date: 1999
- Subjects: Phthalocyanines Platinum group
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4396 , http://hdl.handle.net/10962/d1006151
- Description: The voltammetric behaviour of I-cysteine and other organic compounds such as hydrazine, hydroxylamine and methionine has been studied on GCE modified with phthalocyanine complexes of osmium, rhodium and ruthenium. For cysteine oxidation, the catalytic activity of the electrode was dependent the nature of the axial ligand. When cyanide and dimethylsulphoxide (DMSO) were used as axial ligands, giving (DMSO)(Cl)Rh(III)Pc, [(CN)₂Rh(III)Pc], (DMSO)₂0S(II)Pc and [(DMSO)₂Ru(II)Pc].2DMSO complexes, the peak current increased with repetitive scanning, indicating the increase in catalytic activity of the electrode after each scan. This behaviour was not observed when pyridine was used as axial ligand. The improvement of the catalytic activity of the GCE after the first scan has been attributed to the formation of the dimeric π-cation radical species at the electrode surface. Water soluble phthalocyanine complex ([(CN)₂Os(II)Pc]²⁻) and the tetramethyltetra-pyridinoporphyrazine complexes of Pd(II) and Pt(II), ([Pd(II)2,3Tmtppa(-2)]⁴⁺, [Pd(II)3,4Tmtppa(-2)]⁴⁺, [Pt(II)2,3Tmtppa(-2)]⁴⁺ and [Pt(II)3,4Tmtppa(-2)⁴⁺) have been prepared. [(CN)₂Os(II)Pc]²⁻ is soluble in water at pH greater 4 without the formation of dimers. The [M(II)Tmtppa(-2)]⁴⁺ (M = Pd or Pt) show high solubility in water and are stable only in acidic pHs. The cyclic voltammetry of the MPc and [M(II)Tmtppa(-2)]⁴⁺ complexes prepared, is also reported. The interactions of amino acids I-histidine and I-cysteine with the [M(II)Tmtppa(-2)]⁴⁺ complexes of Pd(II) and Pt(ll) were studied. All the [M(Il)Tmtppa(-2)]⁴⁺ are readily reduced to the monoanion species [M(Il)Tmtppa(-3)]³⁻ in the presence of histidine and cysteine. The rate constants for the interaction of [M(Il)Tmtppa(-2)]⁴⁺ complexes ofPt(II) and Pd(II), with histidine and cysteine range from approximately 2 x 10⁻³ to 0.26 dm³ mol⁻¹ s⁻¹. Kinetics of the interaction of [Co(Il)TSPc]⁴⁻ with amino acids, histidine and cysteine in pH 7.2 buffer were studied. The rate constants were found to be first order in both [Co(II)TSPc]⁴⁻ and the amino acid. The formation of [Co(III)TSPc]³⁻ in the presence of histidine occurred with the rate constant of 0.16 dm³ mol⁻¹ s⁻¹, whereas the formation of the [Co(I)TSPc]⁵⁻ species in the presence of cysteine gave the rate constant of 2.2 dm³ mo⁻¹ s¹. The relative quantum yield (QΔ) for singlet oxygen production by [(CN)₂Os(Il)Pc]²⁻, and [(CN)⁴Ru(II)Pc]²⁻ in DMF using diphenylisobenzofuran (DPBF) and a chemical quencher were determined. The quantum yield values were obtained as 0.39 ± 0.05 , and 0.76 ± 0.02 for [(CN₂Os(II)Pc]²⁻ and [(CN)₂Ru(II)Pc]²⁻ respectively. The differences in quantum yield values have been explained in terms of donor abilities of both the central metal and the axial ligands.
- Full Text:
- Date Issued: 1999
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:
- Date Issued: 1999
- 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:
- Date Issued: 1999
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:
- Date Issued: 1999
- 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:
- Date Issued: 1999
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