Effect of oligomerization on the photochemical properties of silicon octaphenoxyphthalocyanine
- Maree, M David, Nyokong, Tebello
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291542 , vital:56885 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00485-3"
- Description: The photochemical properties of silicon octaphenoxyphthalocyanines (SiOPPc) oligomerized were studied in dimethylsulfoxide (DMSO) solutions. Oligomers containing 2–5 and 9 SiOPPc rings linked with terephthalate linkages were synthesized. Singlet oxygen quantum yields were found to be in the range 0.11–0.34, and increased with the number of rings up to five rings, a decrease in the quantum yield was observed for nine rings. This is explained in terms of the high aggregation of the oligomer containing nine rings.
- Full Text:
- Date Issued: 2001
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291542 , vital:56885 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00485-3"
- Description: The photochemical properties of silicon octaphenoxyphthalocyanines (SiOPPc) oligomerized were studied in dimethylsulfoxide (DMSO) solutions. Oligomers containing 2–5 and 9 SiOPPc rings linked with terephthalate linkages were synthesized. Singlet oxygen quantum yields were found to be in the range 0.11–0.34, and increased with the number of rings up to five rings, a decrease in the quantum yield was observed for nine rings. This is explained in terms of the high aggregation of the oligomer containing nine rings.
- Full Text:
- Date Issued: 2001
Electrooxidation of cresols on carbon electrodes modified with phthalocyaninato and octabutoxyphthalocyaninato cobalt (II) complexes
- Grootboom, Natasha, Nyokong, Tebello
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293207 , vital:57065 , xlink:href="https://doi.org/10.1016/S0003-2670(00)01351-9"
- Description: Glassy carbon electrodes (GCE) modified with cobalt(II) phthalocyanine (CoPc-GCE) and cobalt(II) octabutoxyphthalocyanine (CoOBuPc-GCE) were employed for the electrochemical analysis of ortho-, meta-, and para-cresols. The oxidation potential of p-cresol was shifted towards less positive values to a larger extent, when compared to m- and o-cresols, on CoOBuPc-GCE. However, the GCE was less stable when modified with CoOBuPc than with CoPc. This is explained using the possible differences in the orientation of the adsorbed phthalocyanine molecules on the electrode. Bulk electrolysis of p-cresol at anodic potentials (1.0 V versus Ag|AgCl) on carbon electrodes modified with CoPc resulted in the formation of radicals which coupled to form trimeric products. On unmodified carbon electrodes, coupling of the radicals resulted in dimeric products following bulk electrolysis. The products formed following bulk electrolysis were characterized by liquid chromatography coupled with mass spectrometry.
- Full Text:
- Date Issued: 2001
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293207 , vital:57065 , xlink:href="https://doi.org/10.1016/S0003-2670(00)01351-9"
- Description: Glassy carbon electrodes (GCE) modified with cobalt(II) phthalocyanine (CoPc-GCE) and cobalt(II) octabutoxyphthalocyanine (CoOBuPc-GCE) were employed for the electrochemical analysis of ortho-, meta-, and para-cresols. The oxidation potential of p-cresol was shifted towards less positive values to a larger extent, when compared to m- and o-cresols, on CoOBuPc-GCE. However, the GCE was less stable when modified with CoOBuPc than with CoPc. This is explained using the possible differences in the orientation of the adsorbed phthalocyanine molecules on the electrode. Bulk electrolysis of p-cresol at anodic potentials (1.0 V versus Ag|AgCl) on carbon electrodes modified with CoPc resulted in the formation of radicals which coupled to form trimeric products. On unmodified carbon electrodes, coupling of the radicals resulted in dimeric products following bulk electrolysis. The products formed following bulk electrolysis were characterized by liquid chromatography coupled with mass spectrometry.
- Full Text:
- Date Issued: 2001
Simultaneous voltammetric determination of dopamine and serotonin on carbon paste electrodes modified with iron (II) phthalocyanine complexes
- Oni, Joshua, Nyokong, Tebello
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291603 , vital:56891 , xlink:href="https://doi.org/10.1016/S0003-2670(01)00822-4"
- Description: Carbon paste electrodes (CPE) containing iron(II) phthalocyanine (FePc) and iron(II) tetrasulfophthalocyanine ([FeTSPc]4−) were used for the detection of dopamine (DA) and serotonin (5-HT). Both complexes showed catalytic activity towards the detection of DA and 5-HT. The catalytic activities of [FeTSPc]4− and FePc are compared with those of [CoTSPc]4−, [NiTSPc] 4−, CoPc and NiPc complexes and with those of metal(II) tetraaminophthalocyanines (MTAPc, where M=Ni, Co or Fe) complexes. A significant improvement in the reversibility of the DA oxidation couple was observed on [FeTSPc]4− and FePc modified CPE. [FeTSPc]4− and other [MTSPc]4− modified electrodes inhibited the detection of ascorbic acid (AA), a major interferent in the detection of DA. Simultaneous detection of DA and 5-HT on [FeTSPc]4− modified CPE, in the presence of AA, showed that AA does not interfere with the determination of both species. Also no interference between DA and 5-HT was observed.
- Full Text:
- Date Issued: 2001
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291603 , vital:56891 , xlink:href="https://doi.org/10.1016/S0003-2670(01)00822-4"
- Description: Carbon paste electrodes (CPE) containing iron(II) phthalocyanine (FePc) and iron(II) tetrasulfophthalocyanine ([FeTSPc]4−) were used for the detection of dopamine (DA) and serotonin (5-HT). Both complexes showed catalytic activity towards the detection of DA and 5-HT. The catalytic activities of [FeTSPc]4− and FePc are compared with those of [CoTSPc]4−, [NiTSPc] 4−, CoPc and NiPc complexes and with those of metal(II) tetraaminophthalocyanines (MTAPc, where M=Ni, Co or Fe) complexes. A significant improvement in the reversibility of the DA oxidation couple was observed on [FeTSPc]4− and FePc modified CPE. [FeTSPc]4− and other [MTSPc]4− modified electrodes inhibited the detection of ascorbic acid (AA), a major interferent in the detection of DA. Simultaneous detection of DA and 5-HT on [FeTSPc]4− modified CPE, in the presence of AA, showed that AA does not interfere with the determination of both species. Also no interference between DA and 5-HT was observed.
- Full Text:
- Date Issued: 2001
Construction and characterization of carbon paste ultra-microelectrodes
- Oni, Joshua, Westbroek, Philippe, Nyokong, Tebello
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291531 , vital:56884 , xlink:href="https://doi.org/10.1016/S1388-2481(01)00212-0"
- Description: The construction and characterization of carbon paste ultra-microelectrodes is reported. Besides a disc-shaped electrode, a carbon paste band electrode is studied. It was found that for both electrode configurations steady-state currents were obtained but that with the type of electrode material used for the band electrode, the upper limit of ultra-microelectrode dimensions, which could be used was 100–150 μm. Smaller dimensions for the band electrodes resulted in a high resistance due to the limited conductivity of the carbon paste, when using the optimal paste composition. With cyclic voltammetry, the oxidation of [Fe(CN)6]4− was studied at individual constructed electrodes and at ensembles of individual electrodes. Detection limits of less than 10−6moll−1 were obtained. Using the data of the same curves it was possible to test if the electrodes have errors and about 20% of the constructed electrodes did not pass this test. Finally it was found that these electrodes show good stability.
- Full Text:
- Date Issued: 2001
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291531 , vital:56884 , xlink:href="https://doi.org/10.1016/S1388-2481(01)00212-0"
- Description: The construction and characterization of carbon paste ultra-microelectrodes is reported. Besides a disc-shaped electrode, a carbon paste band electrode is studied. It was found that for both electrode configurations steady-state currents were obtained but that with the type of electrode material used for the band electrode, the upper limit of ultra-microelectrode dimensions, which could be used was 100–150 μm. Smaller dimensions for the band electrodes resulted in a high resistance due to the limited conductivity of the carbon paste, when using the optimal paste composition. With cyclic voltammetry, the oxidation of [Fe(CN)6]4− was studied at individual constructed electrodes and at ensembles of individual electrodes. Detection limits of less than 10−6moll−1 were obtained. Using the data of the same curves it was possible to test if the electrodes have errors and about 20% of the constructed electrodes did not pass this test. Finally it was found that these electrodes show good stability.
- Full Text:
- Date Issued: 2001
Voltammetric determination of nitric oxide on cobalt phthalocyanine modified microelectrodes
- Vilakazi, Sibulelo Lea, Nyokong, Tebello
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291629 , vital:56893 , xlink:href="https://doi.org/10.1016/S0022-0728(01)00583-6"
- Description: The catalytic activity of a carbon fiber microelectrode modified with cobalt phthalocyanine (CoPc-ME) for the detection of nitric oxide in the presence of possible interfering molecules (dopamine and serotonin) is examined. A linear plot is observed for the variation of the catalytic currents with NO concentration in the presence of excess dopamine and serotonin, showing that NO may be determined in the presence of these molecules. However, oxidation currents due to serotonin were found to decrease with increase in NO concentration. The CoPc-ME could also detect NO added to blood or its components, the oxidation currents for NO, however, decreased rapidly with time. The decrease in currents was slower in blood serum, followed by whole blood, with a faster decrease being observed in blood plasma.
- Full Text:
- Date Issued: 2001
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291629 , vital:56893 , xlink:href="https://doi.org/10.1016/S0022-0728(01)00583-6"
- Description: The catalytic activity of a carbon fiber microelectrode modified with cobalt phthalocyanine (CoPc-ME) for the detection of nitric oxide in the presence of possible interfering molecules (dopamine and serotonin) is examined. A linear plot is observed for the variation of the catalytic currents with NO concentration in the presence of excess dopamine and serotonin, showing that NO may be determined in the presence of these molecules. However, oxidation currents due to serotonin were found to decrease with increase in NO concentration. The CoPc-ME could also detect NO added to blood or its components, the oxidation currents for NO, however, decreased rapidly with time. The decrease in currents was slower in blood serum, followed by whole blood, with a faster decrease being observed in blood plasma.
- Full Text:
- Date Issued: 2001
Photochemical studies of tetra-2, 3-pyridinoporphyrazines
- Seotsanyana-Mokhosi, Itumeleng, Kuznetsova, Nina, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291580 , vital:56889 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00427-0"
- Description: Tetra-2,3-pyridinoporphyrazines and the corresponding water-soluble N,N′,N′′,N′′′-tetramethyl-tetra-2,3-pyridinoporphyrazine complexes, containing central metal atoms; M=Ge, Sn, Si and Zn, were synthesized and their photochemical properties were investigated. The reductive quenching of pyridinoporphyrazines excited states, enhanced relative to phthalocyanines, was considered as the first photochemical step of dyes phototransformation in dimethylformamide (DMF) and dimethylsulfoxide (DMSO) solutions under irradiation with visible light. Efficiency of singlet oxygen photosensitization decreases significantly in the row phthalocyanines, unquaternized, quaternized tetra-2,3-pyridinoporphyrazine metallocomplexes.
- Full Text:
- Date Issued: 2001
- Authors: Seotsanyana-Mokhosi, Itumeleng , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291580 , vital:56889 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00427-0"
- Description: Tetra-2,3-pyridinoporphyrazines and the corresponding water-soluble N,N′,N′′,N′′′-tetramethyl-tetra-2,3-pyridinoporphyrazine complexes, containing central metal atoms; M=Ge, Sn, Si and Zn, were synthesized and their photochemical properties were investigated. The reductive quenching of pyridinoporphyrazines excited states, enhanced relative to phthalocyanines, was considered as the first photochemical step of dyes phototransformation in dimethylformamide (DMF) and dimethylsulfoxide (DMSO) solutions under irradiation with visible light. Efficiency of singlet oxygen photosensitization decreases significantly in the row phthalocyanines, unquaternized, quaternized tetra-2,3-pyridinoporphyrazine metallocomplexes.
- Full Text:
- Date Issued: 2001
Comparative photosensitised transformation of polychlorophenols with different sulphonated metallophthalocyanine complexes in aqueous medium
- Ozoemena, Kenneth, Kuznetsova, Nina, Nyokong, Tebello
- Authors: Ozoemena, Kenneth , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291520 , vital:56883 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00243-6"
- Description: The relative efficiencies for the oxidation of trichlorophenol (TCP) and pentachlorophenol (PCP), sensitised by sulphonated phthalocyanine complexes containing Zn, Al, Sn and Si as central metals, were studied in aqueous solutions. For the first time, sulphonated silicon and tin phthalocyanines were synthesised and their activity towards photosensitisation of singlet oxygen and photo-oxidation of polychlorophenols was examined. The efficiency of the sensitised photo-oxidative degradation of polychlorophenols depends not only on singlet oxygen quantum yield of sensitiser, but also on its stability. The influence of substrate structure and the pH of the solution on the photo-oxidation efficiency, as well as on the sensitiser photodegradation were studied. It was found that the contribution of the Type II (singlet oxygen-mediated) mechanism to the relative efficiency of the photosensitised photo-oxidation of the phenol, decreased from phenol to p-chlorophenol, TCP and PCP, whereas Type I radical pathway increased. The results obtained for PCP give evidence that electron transfer from the excited sensitiser to the substrate in its unionised form is responsible for enhanced sensitiser photodegradation.
- Full Text:
- Date Issued: 2001
- Authors: Ozoemena, Kenneth , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291520 , vital:56883 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00243-6"
- Description: The relative efficiencies for the oxidation of trichlorophenol (TCP) and pentachlorophenol (PCP), sensitised by sulphonated phthalocyanine complexes containing Zn, Al, Sn and Si as central metals, were studied in aqueous solutions. For the first time, sulphonated silicon and tin phthalocyanines were synthesised and their activity towards photosensitisation of singlet oxygen and photo-oxidation of polychlorophenols was examined. The efficiency of the sensitised photo-oxidative degradation of polychlorophenols depends not only on singlet oxygen quantum yield of sensitiser, but also on its stability. The influence of substrate structure and the pH of the solution on the photo-oxidation efficiency, as well as on the sensitiser photodegradation were studied. It was found that the contribution of the Type II (singlet oxygen-mediated) mechanism to the relative efficiency of the photosensitised photo-oxidation of the phenol, decreased from phenol to p-chlorophenol, TCP and PCP, whereas Type I radical pathway increased. The results obtained for PCP give evidence that electron transfer from the excited sensitiser to the substrate in its unionised form is responsible for enhanced sensitiser photodegradation.
- Full Text:
- Date Issued: 2001
Silicon octaphenoxyphthalocyanines
- Maree, M David, Kuznetsova, Nina, Nyokong, Tebello
- Authors: Maree, M David , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291591 , vital:56890 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00409-9"
- Description: Photochemical properties of series of axially substituted silicon octaphenoxyphthalocyanines with aryloxy, siloxy, aminoalkoxy, esters of carboxylic acids and sulphonic acid esters residues as axial ligands were studied in dimethylsulfoxide (DMSO) solution. It was found, that under Q-band excitation axial ligands in compounds studied have the propensity to be changed by hydroxyl groups with quantum yields in the range 10−5 to 10−2 depending on the nature of the axial ligand. Axial substituent phototransformation was followed by slow photobleaching of dihydroxysilicon octaphenoxyphthalocyanine (photoproduct) in self-sensitized singlet oxygen mediated oxidation of the macrocycle. Singlet oxygen quantum yields were found to be in the range 0.15–0.20 for majority of the phthalocyanines (Pc) studied.
- Full Text:
- Date Issued: 2001
- Authors: Maree, M David , Kuznetsova, Nina , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291591 , vital:56890 , xlink:href="https://doi.org/10.1016/S1010-6030(01)00409-9"
- Description: Photochemical properties of series of axially substituted silicon octaphenoxyphthalocyanines with aryloxy, siloxy, aminoalkoxy, esters of carboxylic acids and sulphonic acid esters residues as axial ligands were studied in dimethylsulfoxide (DMSO) solution. It was found, that under Q-band excitation axial ligands in compounds studied have the propensity to be changed by hydroxyl groups with quantum yields in the range 10−5 to 10−2 depending on the nature of the axial ligand. Axial substituent phototransformation was followed by slow photobleaching of dihydroxysilicon octaphenoxyphthalocyanine (photoproduct) in self-sensitized singlet oxygen mediated oxidation of the macrocycle. Singlet oxygen quantum yields were found to be in the range 0.15–0.20 for majority of the phthalocyanines (Pc) studied.
- Full Text:
- Date Issued: 2001
Managing regrowth of an indigenous savanna tree species (Terminalia sericea) for fuelwood: The influence of stump dimensions and post-harvest coppice pruning
- Authors: Shackleton, Charlie M
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181672 , vital:43757 , xlink:href="https://doi.org/10.1016/S0961-9534(00)00086-6"
- Description: Most African savannas are subjected to harvesting of wood, especially for fuelwood, charcoal and construction timber. A key attribute of the resilience and productivity of savannas is the ability of damaged trees to regrow from the remaining stump. Survival of the cut stem and growth rate of the resultant coppice shoots is influenced by several factors, including size of the tree, cutting height and the root/shoot ratio after felling. Some of these can be manipulated to maximise subsequent regrowth, but this is little understood for most African savanna species. This study investigated the influence of original tree size, height of cut and post-harvest pruning on regrowth of Terminalia sericea. Regrowth was monitored as the number of coppice shoots, the mean coppice shoot length and the cumulative coppice shoot length per cut stump over four growing seasons. There was a positive relationship between cutting height and number of coppice shoots, but height of cut did not significantly affect mean or cumulative coppice shoot length. Larger stems produced more coppice and had greater mean and cumulative coppice shoot lengths than smaller stems. Post-harvest pruning increased the mean shoot length, but not the cumulative shoot length. After four growing seasons mean shoot length for the single shoot pruning treatment (one shoot left) was 54% greater than for the no prune treatment, whilst the double shoot pruning (two shoots left) was 40% greater. Extrapolated harvest intervals for fuelwood poles were 3–4 years for large stems, 4–5 years for medium-sized stems, and 4–9 years for small stems.
- Full Text:
- Date Issued: 2001
- Authors: Shackleton, Charlie M
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181672 , vital:43757 , xlink:href="https://doi.org/10.1016/S0961-9534(00)00086-6"
- Description: Most African savannas are subjected to harvesting of wood, especially for fuelwood, charcoal and construction timber. A key attribute of the resilience and productivity of savannas is the ability of damaged trees to regrow from the remaining stump. Survival of the cut stem and growth rate of the resultant coppice shoots is influenced by several factors, including size of the tree, cutting height and the root/shoot ratio after felling. Some of these can be manipulated to maximise subsequent regrowth, but this is little understood for most African savanna species. This study investigated the influence of original tree size, height of cut and post-harvest pruning on regrowth of Terminalia sericea. Regrowth was monitored as the number of coppice shoots, the mean coppice shoot length and the cumulative coppice shoot length per cut stump over four growing seasons. There was a positive relationship between cutting height and number of coppice shoots, but height of cut did not significantly affect mean or cumulative coppice shoot length. Larger stems produced more coppice and had greater mean and cumulative coppice shoot lengths than smaller stems. Post-harvest pruning increased the mean shoot length, but not the cumulative shoot length. After four growing seasons mean shoot length for the single shoot pruning treatment (one shoot left) was 54% greater than for the no prune treatment, whilst the double shoot pruning (two shoots left) was 40% greater. Extrapolated harvest intervals for fuelwood poles were 3–4 years for large stems, 4–5 years for medium-sized stems, and 4–9 years for small stems.
- Full Text:
- Date Issued: 2001
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