Study of metallophthalocyanines attached onto pre-modified gold surfaces
- Authors: Mashazi, Philani Nkosinathi
- Date: 2007
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4361 , http://hdl.handle.net/10962/d1005026 , Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Description: Tetra-carboxy acid chloride phthalocyanine complexes of cobalt, iron and manganese were synthesized and characterized using spectroscopic and electrochemical techniques. These complexes were fabricated as thin films on gold electrode following a covalent immobilization and self-assembling methods. Surface electrochemical and spectroscopic characterization showed that these complexes are surface-confined species. The characterization using spectroscopic and electrochemical methods confirmed the formation of thiol and MPc SAMs on gold electrode. The electrocatalytic behaviour of the SAM modified gold electrodes was studied for the detection of L-cysteine and hydrogen peroxide. The limits of detection (LoD) for Lcysteine were of the orders of 10[superscript -7] mol.L[superscript -1] for all the MPc complexes studied and the LoD for hydrogen peroxide at cobalt phthalocyanine modified gold electrode was of the orders of 10[superscript -7]mol.L[superscript -1] for both electrocatalytic oxidation and reduction. The modification process for gold electrodes was reproducible and showed good stability, if stored in pH 4 phosphate buffer solutions and can be used over a long period of time. The cobalt phthalocyanine modified gold electrode was also investigated for the fabrication of glucose oxidase (GOx)-based biosensor and as an electron mediator between the enzyme and gold electrode. The behaviour of the enzyme modified gold electrode towards the detection of glucose was studied and the results gave a limit of detection of the orders of 10[superscript -6] mol.L[superscript -1] with low binding constant (4.8 mM) of enzyme (GOx) to substrate (glucose) referred to as Michaelis-Menten constant. The practical applications, i.e. the real sample analysis and interference studies, for the enzyme modified gold electrodes were investigated. These studies showed that the enzyme electrode is valuable and can be used for glucose detection.
- Full Text:
- Date Issued: 2007
- Authors: Mashazi, Philani Nkosinathi
- Date: 2007
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4361 , http://hdl.handle.net/10962/d1005026 , Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Description: Tetra-carboxy acid chloride phthalocyanine complexes of cobalt, iron and manganese were synthesized and characterized using spectroscopic and electrochemical techniques. These complexes were fabricated as thin films on gold electrode following a covalent immobilization and self-assembling methods. Surface electrochemical and spectroscopic characterization showed that these complexes are surface-confined species. The characterization using spectroscopic and electrochemical methods confirmed the formation of thiol and MPc SAMs on gold electrode. The electrocatalytic behaviour of the SAM modified gold electrodes was studied for the detection of L-cysteine and hydrogen peroxide. The limits of detection (LoD) for Lcysteine were of the orders of 10[superscript -7] mol.L[superscript -1] for all the MPc complexes studied and the LoD for hydrogen peroxide at cobalt phthalocyanine modified gold electrode was of the orders of 10[superscript -7]mol.L[superscript -1] for both electrocatalytic oxidation and reduction. The modification process for gold electrodes was reproducible and showed good stability, if stored in pH 4 phosphate buffer solutions and can be used over a long period of time. The cobalt phthalocyanine modified gold electrode was also investigated for the fabrication of glucose oxidase (GOx)-based biosensor and as an electron mediator between the enzyme and gold electrode. The behaviour of the enzyme modified gold electrode towards the detection of glucose was studied and the results gave a limit of detection of the orders of 10[superscript -6] mol.L[superscript -1] with low binding constant (4.8 mM) of enzyme (GOx) to substrate (glucose) referred to as Michaelis-Menten constant. The practical applications, i.e. the real sample analysis and interference studies, for the enzyme modified gold electrodes were investigated. These studies showed that the enzyme electrode is valuable and can be used for glucose detection.
- Full Text:
- Date Issued: 2007
Substituted phthalocyanines development and self-assembled monolayer sensor studies
- Authors: Matemadombo, Fungisai
- Date: 2006
- Subjects: Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4364 , http://hdl.handle.net/10962/d1005029 , Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Description: Zinc, cobalt and iron phenylthio substituted phthalocyanines have been synthesized and characterized. Cyclic and square wave voltammetry in dimethylformamide containing tetrabutylammonium perchlorate revealed five and six redox processes respectively for the cobalt and iron phenylthio substituted phthalocyanines. These complexes are easier to reduce compared to the corresponding unsubstituted MPc and to butylthio substituted derivatives. Spectroelectrochemistry (in dimethylformamide containing tetrabutylammonium perchlorate) was employed to assign the cyclic voltammetry peaks, and gave spectra characteristic of Fe(I)Pc for reduction of iron phenylthio substituted phthalocyanine and Co(I)Pc for the reduction of cobalt phenylthio substituted phthalocyanine. The spectrum of the former is particularly of importance since such species have not received much attention in literature. Cobalt and iron phenylthio substituted phthalocyanines have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of L-cysteine. Amine substituted cobalt phthalocyanine (CoTAPc) was deposited on gold surfaces by using an interconnecting SAM of mercaptopropionic acid or dithiobis(N-succinimidyl propionate) through the creation of an amide. Reductive and oxidative desorption of the SAMs limit the useful potential window. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. Both SAMs were highly stable and hence will be interesting tools for further research in surface modification and sensor development.
- Full Text:
- Date Issued: 2006
- Authors: Matemadombo, Fungisai
- Date: 2006
- Subjects: Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4364 , http://hdl.handle.net/10962/d1005029 , Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Description: Zinc, cobalt and iron phenylthio substituted phthalocyanines have been synthesized and characterized. Cyclic and square wave voltammetry in dimethylformamide containing tetrabutylammonium perchlorate revealed five and six redox processes respectively for the cobalt and iron phenylthio substituted phthalocyanines. These complexes are easier to reduce compared to the corresponding unsubstituted MPc and to butylthio substituted derivatives. Spectroelectrochemistry (in dimethylformamide containing tetrabutylammonium perchlorate) was employed to assign the cyclic voltammetry peaks, and gave spectra characteristic of Fe(I)Pc for reduction of iron phenylthio substituted phthalocyanine and Co(I)Pc for the reduction of cobalt phenylthio substituted phthalocyanine. The spectrum of the former is particularly of importance since such species have not received much attention in literature. Cobalt and iron phenylthio substituted phthalocyanines have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of L-cysteine. Amine substituted cobalt phthalocyanine (CoTAPc) was deposited on gold surfaces by using an interconnecting SAM of mercaptopropionic acid or dithiobis(N-succinimidyl propionate) through the creation of an amide. Reductive and oxidative desorption of the SAMs limit the useful potential window. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. Both SAMs were highly stable and hence will be interesting tools for further research in surface modification and sensor development.
- Full Text:
- Date Issued: 2006
Synthesis of zinc phthalocyanine derivatives for possible use in photodynamic therapy
- Authors: Matlaba, Pulane Maseleka
- Date: 2003
- Subjects: Photochemotherapy , Electrochemistry , Phthalocyanines , Zinc
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4374 , http://hdl.handle.net/10962/d1005039 , Photochemotherapy , Electrochemistry , Phthalocyanines , Zinc
- Description: The synthesis of symmetrically and unsymmetrically substituted zinc phthalocyanines (ZnPc) derivatives is done according to reported procedures. The unsymmetrical ZnPc derivatives are synthesized by ring expansion of sub-phthalocyanine complexes. Ring substitution is effected with tert-butyl phenol, naphthol, and hydroxybenzoic acid. Comparison of the redox potentials for the complexes substituted with varying numbers of tert-butyl phenol: 1, 2, 3, 6 and 8 show that the complex with the highest number of substituents are more difficult to oxidize and easier to reduce. Water soluble sulphonated ZnPc (ZnPcSn) was prepared. The possibility of using axial ligation to increase the solubility and the photochemical activity of sulphotnated ZnPc in aqueous solutions was investigated. Pyridine, aminopyridyl and bipyridyl were used as axial ligands. When bipyridyl was used as the axial ligand, solubility of the ZnPcSn increased, shown by the increase in the Q-band of the monomer species in solution and the singlet oxygen quantum yields was relatively higher than that of the unligated ZnPcSn. The singlet oxygen quantum yields by the various complexes in DMF using diphenylisobenzofuran as a chemical quencher for organic solvent were determined. Singlet oxygen quantum yields for the unsymmetrically ring substituted complexes range from 0.22 to 0.68. Photobleaching quantum yields are in the order of 10-5, which means that the complexes are relatively photostable.
- Full Text:
- Date Issued: 2003
- Authors: Matlaba, Pulane Maseleka
- Date: 2003
- Subjects: Photochemotherapy , Electrochemistry , Phthalocyanines , Zinc
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4374 , http://hdl.handle.net/10962/d1005039 , Photochemotherapy , Electrochemistry , Phthalocyanines , Zinc
- Description: The synthesis of symmetrically and unsymmetrically substituted zinc phthalocyanines (ZnPc) derivatives is done according to reported procedures. The unsymmetrical ZnPc derivatives are synthesized by ring expansion of sub-phthalocyanine complexes. Ring substitution is effected with tert-butyl phenol, naphthol, and hydroxybenzoic acid. Comparison of the redox potentials for the complexes substituted with varying numbers of tert-butyl phenol: 1, 2, 3, 6 and 8 show that the complex with the highest number of substituents are more difficult to oxidize and easier to reduce. Water soluble sulphonated ZnPc (ZnPcSn) was prepared. The possibility of using axial ligation to increase the solubility and the photochemical activity of sulphotnated ZnPc in aqueous solutions was investigated. Pyridine, aminopyridyl and bipyridyl were used as axial ligands. When bipyridyl was used as the axial ligand, solubility of the ZnPcSn increased, shown by the increase in the Q-band of the monomer species in solution and the singlet oxygen quantum yields was relatively higher than that of the unligated ZnPcSn. The singlet oxygen quantum yields by the various complexes in DMF using diphenylisobenzofuran as a chemical quencher for organic solvent were determined. Singlet oxygen quantum yields for the unsymmetrically ring substituted complexes range from 0.22 to 0.68. Photobleaching quantum yields are in the order of 10-5, which means that the complexes are relatively photostable.
- Full Text:
- Date Issued: 2003
Homogenous and heterogenous catalytic activity of metallophthalocyanines towards electrochemical detection of organic compounds
- Authors: Mafatle, Tsukutlane J P
- Date: 1998
- Subjects: Electrochemistry , Organic compounds , Phenols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4316 , http://hdl.handle.net/10962/d1004974 , Electrochemistry , Organic compounds , Phenols
- Description: Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs Ag/AgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs Ag/AgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.
- Full Text:
- Date Issued: 1998
- Authors: Mafatle, Tsukutlane J P
- Date: 1998
- Subjects: Electrochemistry , Organic compounds , Phenols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4316 , http://hdl.handle.net/10962/d1004974 , Electrochemistry , Organic compounds , Phenols
- Description: Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs Ag/AgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs Ag/AgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.
- Full Text:
- Date Issued: 1998
Liquid junction potentials at mixed electrolyte salt bridges
- Authors: Finkelstein, Noel Phillip
- Date: 1957
- Subjects: Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4473 , http://hdl.handle.net/10962/d1011835 , Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Description: The potentiometric method is one of the most exact techniques of electrochemistry. Its use is widespread in both routine measurements, such as pH determination, and in applications which demand the highest accuracy. Perhaps its severest limitation is the error due to liquid junction potentials. Although this has been the subject of much study, and although various means of combating it have been proposed, it has defied all attempts at a satisfactory solution. Indeed, so serious is the position that it has become the accepted practice in the more accurate fields to abandon altogether the use of potentiometric techniques in favour of others, usually less convenient and otherwise less accurate, when the presence of liquid junctions cannot be avoided. Intro. p. 1.
- Full Text:
- Date Issued: 1957
- Authors: Finkelstein, Noel Phillip
- Date: 1957
- Subjects: Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4473 , http://hdl.handle.net/10962/d1011835 , Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Description: The potentiometric method is one of the most exact techniques of electrochemistry. Its use is widespread in both routine measurements, such as pH determination, and in applications which demand the highest accuracy. Perhaps its severest limitation is the error due to liquid junction potentials. Although this has been the subject of much study, and although various means of combating it have been proposed, it has defied all attempts at a satisfactory solution. Indeed, so serious is the position that it has become the accepted practice in the more accurate fields to abandon altogether the use of potentiometric techniques in favour of others, usually less convenient and otherwise less accurate, when the presence of liquid junctions cannot be avoided. Intro. p. 1.
- Full Text:
- Date Issued: 1957