Surface electrochemistry of iron phthalocyanine axially ligated to 4-mercaptopyridine self-assembled monolayers at gold electrode
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
Synthesis and photophysical properties of a covalently linked porphyrin-phthalocyanine conjugate
- Zhao, Zhixin, Ogunsipe, Abimbola O, Maree, M David, Nyokong, Tebello
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
Synthesis, electrochemical and electrocatalytic behaviour of thiophene-appended cobalt, manganese and zinc phthalocyanine complexes
- Obirai, Joseph, Nyokong, Tebello
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005
Synthesis, photophysicochemical studies of adjacently tetrasubstituted binaphthalo-phthalocyanines
- Seotsanyana-Mokhosi, Itumeleng, Chen, Ji-Yao, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289294 , vital:56616 , xlink:href="https://doi.org/10.1142/S108842460500040X"
- Description: Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.
- Full Text:
- Date Issued: 2005
- Authors: Seotsanyana-Mokhosi, Itumeleng , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289294 , vital:56616 , xlink:href="https://doi.org/10.1142/S108842460500040X"
- Description: Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.
- Full Text:
- Date Issued: 2005
The contribution and direct-use value of livestock to rural livelihoods in the Sand River catchment, South Africa
- Shackleton, Charlie M, Shackleton, Sheona E, Netshiluvhi, T R, Mathabela, F R
- Authors: Shackleton, Charlie M , Shackleton, Sheona E , Netshiluvhi, T R , Mathabela, F R
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181335 , vital:43720 , xlink:href="https://doi.org/10.2989/10220110509485870"
- Description: The productive functions of livestock ownership in communal areas are multipurpose in character, comprising a mix of stock types and a range of goods and services used. When all these multiple uses are accounted for, the cash and direct-use returns of livestock in communal areas can be comparable to commercial systems, although temporally and spatially variable. Yet previous work has generally excluded small stock from such analyses, as well as benefits and costs to non-owning households. This paper presents empirical results of a study in the Sand River catchment, assessing the benefits and costs accruing to owners and non-owners for both cattle and goats within a livelihoods analysis framework. Results indicate that cattle are used for a greater variety of goods and services than are goats. The savings value represented the most important function, followed by milk and then manure. Even if savings value was excluded, cattle ownership made a significant contribution to local livelihoods. Goats also provided a net positive benefit, represented largely by the savings value, followed by meat and cash sales. Non-owners also benefited through donations of manure, milk, draught and meat for free, or at a cheaper rate than alternatives. The majority of non-owners aspired to livestock ownership, although the risk of theft of animals was of growing concern. Averaged across the whole catchment, the net value of goods and services from livestock was just over R400 per hectare, with an annual return to capital of 36%. Cattle contributed the bulk of the value by virtue of their greater numbers and larger size, but on a per kilogramme basis goats provided higher value. Many of the goods and services obtained from livestock were not enumerated in regional or national economic statistics.
- Full Text:
- Date Issued: 2005
- Authors: Shackleton, Charlie M , Shackleton, Sheona E , Netshiluvhi, T R , Mathabela, F R
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181335 , vital:43720 , xlink:href="https://doi.org/10.2989/10220110509485870"
- Description: The productive functions of livestock ownership in communal areas are multipurpose in character, comprising a mix of stock types and a range of goods and services used. When all these multiple uses are accounted for, the cash and direct-use returns of livestock in communal areas can be comparable to commercial systems, although temporally and spatially variable. Yet previous work has generally excluded small stock from such analyses, as well as benefits and costs to non-owning households. This paper presents empirical results of a study in the Sand River catchment, assessing the benefits and costs accruing to owners and non-owners for both cattle and goats within a livelihoods analysis framework. Results indicate that cattle are used for a greater variety of goods and services than are goats. The savings value represented the most important function, followed by milk and then manure. Even if savings value was excluded, cattle ownership made a significant contribution to local livelihoods. Goats also provided a net positive benefit, represented largely by the savings value, followed by meat and cash sales. Non-owners also benefited through donations of manure, milk, draught and meat for free, or at a cheaper rate than alternatives. The majority of non-owners aspired to livestock ownership, although the risk of theft of animals was of growing concern. Averaged across the whole catchment, the net value of goods and services from livestock was just over R400 per hectare, with an annual return to capital of 36%. Cattle contributed the bulk of the value by virtue of their greater numbers and larger size, but on a per kilogramme basis goats provided higher value. Many of the goods and services obtained from livestock were not enumerated in regional or national economic statistics.
- Full Text:
- Date Issued: 2005
The effect of structure on the electrochemical properties of 14 marine pyrroloquinoline metabolites
- Antunes, Edith M, Maree, Suzanne E, Nyokong, Tebello, Davies-Coleman, Mike T, Maree, M David
- Authors: Antunes, Edith M , Maree, Suzanne E , Nyokong, Tebello , Davies-Coleman, Mike T , Maree, M David
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286126 , vital:56242 , xlink:href="https://doi.org/10.3184/030823405775146915"
- Description: The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules.
- Full Text:
- Date Issued: 2005
- Authors: Antunes, Edith M , Maree, Suzanne E , Nyokong, Tebello , Davies-Coleman, Mike T , Maree, M David
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286126 , vital:56242 , xlink:href="https://doi.org/10.3184/030823405775146915"
- Description: The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules.
- Full Text:
- Date Issued: 2005
Towards a better grasp of what matters in view of ‘the posts’
- O'Donoghue, Rob, Lotz-Sisitka, Heila
- Authors: O'Donoghue, Rob , Lotz-Sisitka, Heila
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182693 , vital:43854 , xlink:href="https://doi.org/10.1080/13504620500169593"
- Description: This response to McKenzie suggests that the issues of representivity, legitimacy and politics, inscribed within an institutional continuism characteristic of modernity within the McKenzie discourse, could well be recast within a reflexive view informed by insights derived with developing social theory. It briefly overviews the struggle for human agency that played out within the deconstructive engagements of the posts and probes how perspectives in social theory are opening the way for a break with features of environmental education as an institutional field. The review points to a reconstituting of the idea of environmental education research from scholastic field of/for environmental awareness and sustainable development, to a reflexive engagement within processes of social reproduction and reorientation in a changing world. A shift such as this would constitute a subtle change in a developing field of research, to situated design decisions of reflexive engagement (research) in social fields constituted within developing cultural contexts of risk.
- Full Text:
- Date Issued: 2005
- Authors: O'Donoghue, Rob , Lotz-Sisitka, Heila
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182693 , vital:43854 , xlink:href="https://doi.org/10.1080/13504620500169593"
- Description: This response to McKenzie suggests that the issues of representivity, legitimacy and politics, inscribed within an institutional continuism characteristic of modernity within the McKenzie discourse, could well be recast within a reflexive view informed by insights derived with developing social theory. It briefly overviews the struggle for human agency that played out within the deconstructive engagements of the posts and probes how perspectives in social theory are opening the way for a break with features of environmental education as an institutional field. The review points to a reconstituting of the idea of environmental education research from scholastic field of/for environmental awareness and sustainable development, to a reflexive engagement within processes of social reproduction and reorientation in a changing world. A shift such as this would constitute a subtle change in a developing field of research, to situated design decisions of reflexive engagement (research) in social fields constituted within developing cultural contexts of risk.
- Full Text:
- Date Issued: 2005