Facile electrocatalytic oxidation of diuron on polymerized nickel hydroxo tetraamino-phthalocyanine modified glassy carbon electrodes
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261269 , vital:53379 , xlink:href="https://doi.org/10.1016/j.talanta.2010.02.037"
- Description: The facile electro-oxidation of diuron occurred at a glassy carbon electrode (GCE) modified with polymerized nickel tetraamino-phthalocyanine (NiTAPc), containing O–Ni–O bridges represented as poly-Ni(OH)TAPc-GCE. The oxidation of diuron occurred at a potential which is 60 mV less than that of poly-NiTAPc (without O–Ni–O bridges) and was accompanied by enhanced catalytic currents. The catalytic rate constant and the diffusion constant were found to be 5.91 × 102 mol−1 L s−1 and 6.43 × 10−6 cm2 s−1, respectively. The linear concentration range of diuron was 3.0 × 10−5 to 3.5 × 10−4 mol L−1 with a limit of detection (LOD) of 3.3 × 10−7 mol L−1 (3δ notation) and a sensitivity of 12.9 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2010
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261269 , vital:53379 , xlink:href="https://doi.org/10.1016/j.talanta.2010.02.037"
- Description: The facile electro-oxidation of diuron occurred at a glassy carbon electrode (GCE) modified with polymerized nickel tetraamino-phthalocyanine (NiTAPc), containing O–Ni–O bridges represented as poly-Ni(OH)TAPc-GCE. The oxidation of diuron occurred at a potential which is 60 mV less than that of poly-NiTAPc (without O–Ni–O bridges) and was accompanied by enhanced catalytic currents. The catalytic rate constant and the diffusion constant were found to be 5.91 × 102 mol−1 L s−1 and 6.43 × 10−6 cm2 s−1, respectively. The linear concentration range of diuron was 3.0 × 10−5 to 3.5 × 10−4 mol L−1 with a limit of detection (LOD) of 3.3 × 10−7 mol L−1 (3δ notation) and a sensitivity of 12.9 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2010
Fluorescence quenching and energy transfer in conjugates of quantum dots with zinc and indium tetraamino phthalocyanines
- Britton, Jonathan, Antunes, Edith M, Nyokong, Tebello
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262638 , vital:53539 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.013"
- Description: CdTe QDs capped with mercapto propionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104 M−1. High energy transfer efficiencies were obtained in some cases (as high as 93%), due to the low donor to acceptor distances.
- Full Text:
- Date Issued: 2010
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262638 , vital:53539 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.013"
- Description: CdTe QDs capped with mercapto propionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104 M−1. High energy transfer efficiencies were obtained in some cases (as high as 93%), due to the low donor to acceptor distances.
- Full Text:
- Date Issued: 2010
Characterization of amine-functionalized single-walled carbon nanotube-low symmetry phthalocyanine conjugates
- Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7237 , http://hdl.handle.net/10962/d1019688
- Description: Functionalization of single-walled carbon nanotubes (SWCNTs) with amine groups using a previously developed diazonium approach, followed by reaction with a carboxylic acid moiety allows direct attachment by an amide bond. We have developed a new SWCNT-low symmetry phthalocyanine conjugate using this approach, using dicyclohexylcarbodiimide as an activating agent to facilitate formation of an amide bond to give a covalently linked conjugate. A conjugate formed by non-covalent attachment has been used for a comparative investigation by FT-IR, Raman, and UV–Vis spectroscopies, and thermal gravimetric analysis. The fluorescence of the phthalocyanine is quenched in the conjugate. , Original publication is available at http://dx.doi.org/10.1016/j.carbon.2010.04.015
- Full Text: false
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7237 , http://hdl.handle.net/10962/d1019688
- Description: Functionalization of single-walled carbon nanotubes (SWCNTs) with amine groups using a previously developed diazonium approach, followed by reaction with a carboxylic acid moiety allows direct attachment by an amide bond. We have developed a new SWCNT-low symmetry phthalocyanine conjugate using this approach, using dicyclohexylcarbodiimide as an activating agent to facilitate formation of an amide bond to give a covalently linked conjugate. A conjugate formed by non-covalent attachment has been used for a comparative investigation by FT-IR, Raman, and UV–Vis spectroscopies, and thermal gravimetric analysis. The fluorescence of the phthalocyanine is quenched in the conjugate. , Original publication is available at http://dx.doi.org/10.1016/j.carbon.2010.04.015
- Full Text: false
The use and appreciation of botanical gardens as urban green spaces in South Africa
- Ward, Catherine D, Parker, Caitlin M, Shackleton, Charlie M
- Authors: Ward, Catherine D , Parker, Caitlin M , Shackleton, Charlie M
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181146 , vital:43702 , xlink:href="https://doi.org/10.1016/j.ufug.2009.11.001"
- Description: There are few formal studies on the contribution of botanical gardens as urban green spaces, particularly within developing countries. Therefore, this paper reports on an assessment of the use and appreciation of botanical gardens as urban green spaces in South Africa. Users and staff were surveyed in six national botanical gardens. The gardens provided numerous benefits in terms of conservation, education and recreation. However, the people using the gardens were not demographically representative of the general population of the surrounding city or town. Generally, most of the visitors were middle- to old-aged, well-educated professionals with medium to high incomes. Most were white and English was their home language. There was an even gender representation. Most visited only a few times per year. The majority of users visited the gardens for recreation and psychological reasons rather than educational ones. However, the staff of each garden placed emphasis on education in the gardens and amongst surrounding schools. Most visitors appreciated the conservation dimensions of botanical gardens, and felt that there was insufficient public green space in their town or city. Understanding how people perceive and use the botanical gardens of South Africa is important to inform future research and strategies regarding the conservation of urban green space within a developing country.
- Full Text:
- Date Issued: 2010
- Authors: Ward, Catherine D , Parker, Caitlin M , Shackleton, Charlie M
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181146 , vital:43702 , xlink:href="https://doi.org/10.1016/j.ufug.2009.11.001"
- Description: There are few formal studies on the contribution of botanical gardens as urban green spaces, particularly within developing countries. Therefore, this paper reports on an assessment of the use and appreciation of botanical gardens as urban green spaces in South Africa. Users and staff were surveyed in six national botanical gardens. The gardens provided numerous benefits in terms of conservation, education and recreation. However, the people using the gardens were not demographically representative of the general population of the surrounding city or town. Generally, most of the visitors were middle- to old-aged, well-educated professionals with medium to high incomes. Most were white and English was their home language. There was an even gender representation. Most visited only a few times per year. The majority of users visited the gardens for recreation and psychological reasons rather than educational ones. However, the staff of each garden placed emphasis on education in the gardens and amongst surrounding schools. Most visitors appreciated the conservation dimensions of botanical gardens, and felt that there was insufficient public green space in their town or city. Understanding how people perceive and use the botanical gardens of South Africa is important to inform future research and strategies regarding the conservation of urban green space within a developing country.
- Full Text:
- Date Issued: 2010
The valuation of campus built heritage from the student perspective: comparative analysis of Rhodes University in South Africa and St. Mary’s College of Maryland in the United States
- Poor, Joan P, Snowball, Jeanette D
- Authors: Poor, Joan P , Snowball, Jeanette D
- Date: 2010
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/67488 , vital:29102 , https://doi.org/10.1016/j.culher.2009.05.002
- Description: Pre-print , Many universities and colleges around the world have done extensive surveys of their campus built heritage resources. A detailed description and accounting of a campus's built heritage, landscape heritage and archaeology, are often used for historic preservation planning, and sustaining built culture is also an important aspect of campus master planning of future buildings. Such institutions of higher education have deep historical roots, in Europe it is not uncommon for buildings to be dated prior to the sixteenth century. In countries where European colonies were established, institutions of higher education often date to the eighteenth and early nineteenth centuries. Once students have arrived at their chosen campus, however, except for perhaps the first week orientation rituals, do the students actually develop ties to their campus built heritage? This research investigates the knowledge students possess of their respective campus built heritage and the importance of built heritage as a legacy to them. Two institutions are included in this study in an effort of draw comparative assessments. A student questionnaire was administered at Rhodes University in South Africa and St. Mary's College of Maryland in the United States during April 2008. Results indicate students on both campuses place positive intrinsic value on their respective campus built heritage. Just over half (52%) of Rhodes students and about 68% of St. Mary's students were willing to pay some positive amount to protect campus built heritage. Empirical probit model results combining the data from both institutions found that current student knowledge of their respective campus built heritage did not positively relate to the value they place on preservation, even though the visual identity was significant for students and influenced their decision to attend the particular institution. The lack of significance regarding a racial variable coefficient estimate suggests that the use of an institution's visual identity in terms of built heritage may have important marketing implications, particularly in cases where universities or colleges are trying to attract students from more diverse backgrounds. We found no significant relationships between willingness to pay to preserve an institution's built heritage and the demographic variables included in our empirical model. Fundraising data analysis includes positive willingness to pay for conserving built heritage, yet funding for new construction was not significant.
- Full Text:
- Date Issued: 2010
- Authors: Poor, Joan P , Snowball, Jeanette D
- Date: 2010
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/67488 , vital:29102 , https://doi.org/10.1016/j.culher.2009.05.002
- Description: Pre-print , Many universities and colleges around the world have done extensive surveys of their campus built heritage resources. A detailed description and accounting of a campus's built heritage, landscape heritage and archaeology, are often used for historic preservation planning, and sustaining built culture is also an important aspect of campus master planning of future buildings. Such institutions of higher education have deep historical roots, in Europe it is not uncommon for buildings to be dated prior to the sixteenth century. In countries where European colonies were established, institutions of higher education often date to the eighteenth and early nineteenth centuries. Once students have arrived at their chosen campus, however, except for perhaps the first week orientation rituals, do the students actually develop ties to their campus built heritage? This research investigates the knowledge students possess of their respective campus built heritage and the importance of built heritage as a legacy to them. Two institutions are included in this study in an effort of draw comparative assessments. A student questionnaire was administered at Rhodes University in South Africa and St. Mary's College of Maryland in the United States during April 2008. Results indicate students on both campuses place positive intrinsic value on their respective campus built heritage. Just over half (52%) of Rhodes students and about 68% of St. Mary's students were willing to pay some positive amount to protect campus built heritage. Empirical probit model results combining the data from both institutions found that current student knowledge of their respective campus built heritage did not positively relate to the value they place on preservation, even though the visual identity was significant for students and influenced their decision to attend the particular institution. The lack of significance regarding a racial variable coefficient estimate suggests that the use of an institution's visual identity in terms of built heritage may have important marketing implications, particularly in cases where universities or colleges are trying to attract students from more diverse backgrounds. We found no significant relationships between willingness to pay to preserve an institution's built heritage and the demographic variables included in our empirical model. Fundraising data analysis includes positive willingness to pay for conserving built heritage, yet funding for new construction was not significant.
- Full Text:
- Date Issued: 2010
The effects of point of substitution on the formation of manganese phthalocyanine-based molecular materials
- Akinbulu, Isaac Adebayo, Khene, Samson, Nyokong, Tebello
- Authors: Akinbulu, Isaac Adebayo , Khene, Samson , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249103 , vital:51778 , xlink:href="https://doi.org/10.1016/j.tsf.2010.08.145"
- Description: Molecular films of manganese phthalocyanine (MnPc) complexes, tetra-substituted with 2-diethylaminoethanethio at the peripheral (Mn(OAc)-β-TDEAETPc, 1) and non-peripheral (Mn(OAc)-α-TDEAETPc, 2) positions were formed on glassy carbon electrode by electropolymerization and electrodeposition respectively. Atomic force microscopy images confirmed the presence of the films and revealed significant morphological differences. The films exhibited an electrocatalytic activity towards the oxidation of the insecticide, bendiocarb. Hydrodynamic technique, using rotating disc electrode voltammetry, was used to investigate the kinetics of electro-oxidation of the insecticide. Morphological differences of the films significantly influenced kinetic parameters. Values of Tafel slopes, obtained from Tafel plots, suggested that catalysis of bendiocarb occurred via outer sphere mechanism.
- Full Text:
- Date Issued: 2010
- Authors: Akinbulu, Isaac Adebayo , Khene, Samson , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249103 , vital:51778 , xlink:href="https://doi.org/10.1016/j.tsf.2010.08.145"
- Description: Molecular films of manganese phthalocyanine (MnPc) complexes, tetra-substituted with 2-diethylaminoethanethio at the peripheral (Mn(OAc)-β-TDEAETPc, 1) and non-peripheral (Mn(OAc)-α-TDEAETPc, 2) positions were formed on glassy carbon electrode by electropolymerization and electrodeposition respectively. Atomic force microscopy images confirmed the presence of the films and revealed significant morphological differences. The films exhibited an electrocatalytic activity towards the oxidation of the insecticide, bendiocarb. Hydrodynamic technique, using rotating disc electrode voltammetry, was used to investigate the kinetics of electro-oxidation of the insecticide. Morphological differences of the films significantly influenced kinetic parameters. Values of Tafel slopes, obtained from Tafel plots, suggested that catalysis of bendiocarb occurred via outer sphere mechanism.
- Full Text:
- Date Issued: 2010
Photophysical study of a covalently linked quantum dot–low symmetry phthalocyanine conjugate
- Chidawanyika, Wadzanai J U, Litwinski, Christian, Antunes, Edith M, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
- Full Text:
- Date Issued: 2010
- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
- Full Text:
- Date Issued: 2010
The synthesis and fluorescence behaviour of phthalocyanines unsymmetrically substituted with naphthol and carboxy groups
- Nombona, Nolwazi, Antunes, Edith M, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261534 , vital:53418 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.11.010"
- Description: Unsymmetrically substituted phthalocyanines 8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanine, [8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanato]zinc(II), 8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyanine and [8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenoxy)phthalocyanato]zinc(II) were prepared using the mixed phthalonitrile cyclotetramerization of 3-(1-naphthoxy) phthalonitrile with a carboxylic acid phthalonitrile. The phthalocyanines were separated using column chromatography employing a mixture of THF, ammonia and water. The novel compounds were characterized using UV–Vis, IR, 1H NMR and mass spectrometry as well as elemental analysis. Fluorescence quantum yields were found to range from 0.05 to 0.16.
- Full Text:
- Date Issued: 2010
- Authors: Nombona, Nolwazi , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261534 , vital:53418 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.11.010"
- Description: Unsymmetrically substituted phthalocyanines 8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanine, [8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanato]zinc(II), 8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyanine and [8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenoxy)phthalocyanato]zinc(II) were prepared using the mixed phthalonitrile cyclotetramerization of 3-(1-naphthoxy) phthalonitrile with a carboxylic acid phthalonitrile. The phthalocyanines were separated using column chromatography employing a mixture of THF, ammonia and water. The novel compounds were characterized using UV–Vis, IR, 1H NMR and mass spectrometry as well as elemental analysis. Fluorescence quantum yields were found to range from 0.05 to 0.16.
- Full Text:
- Date Issued: 2010
Towards the synthesis of coumarin derivatives as potential dual-action HIV-1 protease and reverse transcriptase inhibitors
- Olomola, Temitope O, Klein, Rosalyn, Lobb, Kevin A, Sayed, Yasien, Kaye, Perry T
- Authors: Olomola, Temitope O , Klein, Rosalyn , Lobb, Kevin A , Sayed, Yasien , Kaye, Perry T
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/448963 , vital:74774 , xlink:href="https://doi.org/10.1016/j.tetlet.2010.09.121"
- Description: 3-(Chloromethyl)coumarins, obtained via acid-catalysed cyclisation of salicylaldehyde-derived Baylis– Hillman adducts, have been treated with propargylamine; reaction of the resulting 3-alkynylmethylcoumarins with azidothymidine (AZT) in the presence of a Cu(I) catalyst has afforded a series of cycloaddition products for evaluation, in their own right, as potential dual-action HIV-1 protease and non-nucleoside reverse transcriptase inhibitors, and as scaffolds for further structural elaboration.
- Full Text:
- Date Issued: 2010
- Authors: Olomola, Temitope O , Klein, Rosalyn , Lobb, Kevin A , Sayed, Yasien , Kaye, Perry T
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/448963 , vital:74774 , xlink:href="https://doi.org/10.1016/j.tetlet.2010.09.121"
- Description: 3-(Chloromethyl)coumarins, obtained via acid-catalysed cyclisation of salicylaldehyde-derived Baylis– Hillman adducts, have been treated with propargylamine; reaction of the resulting 3-alkynylmethylcoumarins with azidothymidine (AZT) in the presence of a Cu(I) catalyst has afforded a series of cycloaddition products for evaluation, in their own right, as potential dual-action HIV-1 protease and non-nucleoside reverse transcriptase inhibitors, and as scaffolds for further structural elaboration.
- Full Text:
- Date Issued: 2010
31P NMR kinetic study of the tandem cleavage of phosphonate esters by bromotrimethylsilane
- Conibear, Anne C, Lobb, Kevin A, Kaye, Perry T
- Authors: Conibear, Anne C , Lobb, Kevin A , Kaye, Perry T
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449304 , vital:74810 , xlink:href="https://doi.org/10.1016/j.tet.2010.08.058"
- Description: 1H and 31P NMR methods have been used to access rate constants and activation parameters for each of the consecutive second-order silylation reactions involved in the overall transformation (1a→3a→4a), while computational optimisation of the rate constants obtained from the initial, linear phase of each reaction has permitted an excellent fit with the experimental data for the entire course of the reaction.
- Full Text:
- Date Issued: 2010
- Authors: Conibear, Anne C , Lobb, Kevin A , Kaye, Perry T
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449304 , vital:74810 , xlink:href="https://doi.org/10.1016/j.tet.2010.08.058"
- Description: 1H and 31P NMR methods have been used to access rate constants and activation parameters for each of the consecutive second-order silylation reactions involved in the overall transformation (1a→3a→4a), while computational optimisation of the rate constants obtained from the initial, linear phase of each reaction has permitted an excellent fit with the experimental data for the entire course of the reaction.
- Full Text:
- Date Issued: 2010
Interaction between nickel hydroxy phthalocyanine derivatives with p-chlorophenol
- Khene, Samson, Lobb, Kevin A, Nyokong, Tebello
- Authors: Khene, Samson , Lobb, Kevin A , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248461 , vital:51688 , xlink:href="https://doi.org/10.1016/j.electacta.2010.10.007"
- Description: In this work the interaction between peripherally (β) substituted nickel tetrahydroxyphthalocyanines (β-NiPc(OH)4 and β-Ni(O)Pc(OH)4) with p-chlorophenol is theoretically rationalised by performing calculations at B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and p-chlorophenol, in order to determine the reactive sites involved when p-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: ads-α-NiPc(OH)8-OPGE (OPGE = ordinary poly graphite electrode), ads-α-NiPc(OH)4-OPGE and ads-β-NiPc(OH)4-OPGE are compared with those of the polymerized counterparts: poly-α-Ni(O)Pc(OH)8-OPGE, poly-α-NiPc(OH)4-OPGE and poly-β-NiPc(OH)4-OPGE, respectively.
- Full Text:
- Date Issued: 2010
- Authors: Khene, Samson , Lobb, Kevin A , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248461 , vital:51688 , xlink:href="https://doi.org/10.1016/j.electacta.2010.10.007"
- Description: In this work the interaction between peripherally (β) substituted nickel tetrahydroxyphthalocyanines (β-NiPc(OH)4 and β-Ni(O)Pc(OH)4) with p-chlorophenol is theoretically rationalised by performing calculations at B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and p-chlorophenol, in order to determine the reactive sites involved when p-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: ads-α-NiPc(OH)8-OPGE (OPGE = ordinary poly graphite electrode), ads-α-NiPc(OH)4-OPGE and ads-β-NiPc(OH)4-OPGE are compared with those of the polymerized counterparts: poly-α-Ni(O)Pc(OH)8-OPGE, poly-α-NiPc(OH)4-OPGE and poly-β-NiPc(OH)4-OPGE, respectively.
- Full Text:
- Date Issued: 2010
Determining spatial changes in the diet of nearshore suspension-feeders along the South African coastline: stable isotope and fatty acid signatures
- Allan, E Louise, Ambrose, Shan T, Richoux, Nicole B, Froneman, P William
- Authors: Allan, E Louise , Ambrose, Shan T , Richoux, Nicole B , Froneman, P William
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457945 , vital:75697 , xlink:href="https://doi.org/10.1016/j.ecss.2010.02.004"
- Description: Mesoscale oceanographic features, such as upwellings, are known to play an important role in regulating the structure and productivity of nearshore marine communities. Stable isotope (δ13C and δ15N) and fatty acid analyses were employed to assess the influence of an upwelling cell along the south-eastern coastline of southern Africa on the diet of the mussel, Perna perna. Eight sites were sampled: two upstream, three in the vicinity and three downstream of the upwelling cell. Stable isotope and fatty acid signatures indicated that the mussels consumed a diet of detritus derived mainly from macroalgae, diatoms and dinoflagellates. One-way ANOVA on the δ13C and δ15N signatures and the principal component analysis of the fatty acid profiles of the mussels identified distinct groups corresponding to the above mentioned regions. The proportion of diatom biomarkers in the fatty acid profiles decreased downstream of the upwelling region while the proportion of dinoflagellate biomarkers increased. Upwelling regions are typically associated with elevated levels of productivity; however, these systems usually become silicon depleted and result in the replacement of diatoms with dinoflagellates. The highest proportions of the dinoflagellate markers were recorded in the two furthest sites downstream of the upwelling cell. The spatial variation in the diet of the mussels, therefore, appears to reflect the presence of the upwelling cell in the nearshore biology of the region.
- Full Text:
- Date Issued: 2010
- Authors: Allan, E Louise , Ambrose, Shan T , Richoux, Nicole B , Froneman, P William
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457945 , vital:75697 , xlink:href="https://doi.org/10.1016/j.ecss.2010.02.004"
- Description: Mesoscale oceanographic features, such as upwellings, are known to play an important role in regulating the structure and productivity of nearshore marine communities. Stable isotope (δ13C and δ15N) and fatty acid analyses were employed to assess the influence of an upwelling cell along the south-eastern coastline of southern Africa on the diet of the mussel, Perna perna. Eight sites were sampled: two upstream, three in the vicinity and three downstream of the upwelling cell. Stable isotope and fatty acid signatures indicated that the mussels consumed a diet of detritus derived mainly from macroalgae, diatoms and dinoflagellates. One-way ANOVA on the δ13C and δ15N signatures and the principal component analysis of the fatty acid profiles of the mussels identified distinct groups corresponding to the above mentioned regions. The proportion of diatom biomarkers in the fatty acid profiles decreased downstream of the upwelling region while the proportion of dinoflagellate biomarkers increased. Upwelling regions are typically associated with elevated levels of productivity; however, these systems usually become silicon depleted and result in the replacement of diatoms with dinoflagellates. The highest proportions of the dinoflagellate markers were recorded in the two furthest sites downstream of the upwelling cell. The spatial variation in the diet of the mussels, therefore, appears to reflect the presence of the upwelling cell in the nearshore biology of the region.
- Full Text:
- Date Issued: 2010
Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions
- Zagal, José H, Griveau, Sophie J, Silva, Francisco, Nyokong, Tebello, Bedioui, Fethi
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
- Date Issued: 2010
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
- Date Issued: 2010
Spectroscopic behavior of cationic metallophthalocyanines in the presence of anionic quantum dots
- Idowu, Mopelola A I, Nyokong, Tebello
- Authors: Idowu, Mopelola A I , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262699 , vital:53545 , xlink:href="https://doi.org/10.1016/j.saa.2009.10.050"
- Description: The interactions and spectroscopic properties between cationic zinc phthalocyanine derivatives (peripherally and non-peripherally tetrasubstituted and peripherally octa substituted with 2-diethylmethylaminoethylsulfanyl (βTZnPc, αTZnPc and βOZnPc)) and CdTe core quantum dots (QDs) capped with mercaptopropionic acid or thioglycolic acid (represented as CdTe@MPA and CdTe@TGA, respectively) have been studied in methanol:water mixture. Strong coupling of MPcs was deduced from the interaction since the UV–vis spectroscopic studies of the ground state complex formed on mixing both components showed loss of the phthalocyanine monomeric band with the formation of a dimeric band (spectrum of aggregated species). The dimerization constants were of the order of 104 M−1.
- Full Text:
- Date Issued: 2010
- Authors: Idowu, Mopelola A I , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262699 , vital:53545 , xlink:href="https://doi.org/10.1016/j.saa.2009.10.050"
- Description: The interactions and spectroscopic properties between cationic zinc phthalocyanine derivatives (peripherally and non-peripherally tetrasubstituted and peripherally octa substituted with 2-diethylmethylaminoethylsulfanyl (βTZnPc, αTZnPc and βOZnPc)) and CdTe core quantum dots (QDs) capped with mercaptopropionic acid or thioglycolic acid (represented as CdTe@MPA and CdTe@TGA, respectively) have been studied in methanol:water mixture. Strong coupling of MPcs was deduced from the interaction since the UV–vis spectroscopic studies of the ground state complex formed on mixing both components showed loss of the phthalocyanine monomeric band with the formation of a dimeric band (spectrum of aggregated species). The dimerization constants were of the order of 104 M−1.
- Full Text:
- Date Issued: 2010