Azide-derivatized gold nanosphere “clicked” to indium and zinc phthalocyanines for improved nonlinear optical limiting
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188249 , vital:44738 , xlink:href="https://doi.org/10.1016/j.molstruc.2017.01.088"
- Description: We report on the conjugation of azide-derivatized gold nanoparticles (AuNPs) to alkyne moieties of ZnPc and InPc via azide-alkyne Huisgen cycloaddition reaction to form phthalocyanines-AuNPs (MPc-AuNPs) conjugates. The detailed structural characterizations of the composites were in good agreement with the expected results. The nonlinear absorption coefficients and other nonlinear optical limiting parameters were almost two times larger for the conjugates compared to free phthalocyanines. We established direct relationship between improved photophysical characterizations and enhanced nonlinear effects of reverse saturable absorption mechanisms favoured by excited triplet absorption of the phthalocyanines in the presence of AuNPs. The combination of InPc with AuNPs resulted in the lowest limiting intensity value of 0.06 J/cm2, hence the best performance in terms of optical limiting.
- Full Text:
- Date Issued: 2017
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188249 , vital:44738 , xlink:href="https://doi.org/10.1016/j.molstruc.2017.01.088"
- Description: We report on the conjugation of azide-derivatized gold nanoparticles (AuNPs) to alkyne moieties of ZnPc and InPc via azide-alkyne Huisgen cycloaddition reaction to form phthalocyanines-AuNPs (MPc-AuNPs) conjugates. The detailed structural characterizations of the composites were in good agreement with the expected results. The nonlinear absorption coefficients and other nonlinear optical limiting parameters were almost two times larger for the conjugates compared to free phthalocyanines. We established direct relationship between improved photophysical characterizations and enhanced nonlinear effects of reverse saturable absorption mechanisms favoured by excited triplet absorption of the phthalocyanines in the presence of AuNPs. The combination of InPc with AuNPs resulted in the lowest limiting intensity value of 0.06 J/cm2, hence the best performance in terms of optical limiting.
- Full Text:
- Date Issued: 2017
Ball-type phthalocyanines and reduced graphene oxide nanoparticles as separate and combined corrosion inhibitors of aluminium in HCl
- Nnaji, Nnaemeka, Nawji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nawji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185421 , vital:44385 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130279"
- Description: Corrosion inhibition performances and adsorption behaviour at the aluminum-HCl solution interface were investigated for reduced graphene oxide nanosheets (rGONS), tetrakis-[4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)] (diphthalocyaninato gallium (III) chloride) (2) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium(III) chloride) (1). Corrosion inhibition effects of rGONS, 1 and 2 were evaluated alone and in combination in 1.0 M hydrochloric acid solution using electrochemical techniques. The mechanism of aluminum corrosion inhibition revealed predominantly anodic character for rGONS and predominantly cathodic character for 1, 2, and conjugates with rGONS . The polarization technique gave inhibition efficiency values of 96.5% and 96.9% respectively for 1 and 2, which increased in the presence of rGONS to 97.4% and 98.1%, respectively, for the highest concentrations of 1 and 2. Scanning electron microscopy revealed effective metal surface protection by the inhibitors by formation of protective films.
- Full Text:
- Date Issued: 2021
- Authors: Nnaji, Nnaemeka , Nawji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185421 , vital:44385 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130279"
- Description: Corrosion inhibition performances and adsorption behaviour at the aluminum-HCl solution interface were investigated for reduced graphene oxide nanosheets (rGONS), tetrakis-[4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)] (diphthalocyaninato gallium (III) chloride) (2) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium(III) chloride) (1). Corrosion inhibition effects of rGONS, 1 and 2 were evaluated alone and in combination in 1.0 M hydrochloric acid solution using electrochemical techniques. The mechanism of aluminum corrosion inhibition revealed predominantly anodic character for rGONS and predominantly cathodic character for 1, 2, and conjugates with rGONS . The polarization technique gave inhibition efficiency values of 96.5% and 96.9% respectively for 1 and 2, which increased in the presence of rGONS to 97.4% and 98.1%, respectively, for the highest concentrations of 1 and 2. Scanning electron microscopy revealed effective metal surface protection by the inhibitors by formation of protective films.
- Full Text:
- Date Issued: 2021
Beyond benefit sharing: Place attachment and the importance of access to protected areas for surrounding communities
- Cundill, Georgina, Bezerra, Joana C, de Vos, Alta, Ntingana, Nokuthula
- Authors: Cundill, Georgina , Bezerra, Joana C , de Vos, Alta , Ntingana, Nokuthula
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416265 , vital:71334 , xlink:href="https://doi.org/10.1016/j.ecoser.2017.03.011"
- Description: The concept of place attachment can assist to integrate relational values into ecosystem service research, and assist us to rethink the notion of benefits in contemporary protected area thinking. We present a case study from South Africa, where the concept of two-dimensional place attachment was used to understand the relationship between a protected area and a land claimant community that now owns part of this protected area but does not have physical access to the land. A place attachment lens helps refocus access to protected areas as cornerstone to long term sustainability of such areas. Such access must be considered in the context of spatially and economically differentiated users, including a focus on trade-offs between such users. Our findings highlight that when communities previously displaced from protected areas respond to offers of ‘benefit sharing’ with demands for access and recognition as land owners, they are asking for a recognition of relational values, and identity, based on close interaction with nature. A place attachment and relational values perspective raises questions about the extent to which traditional conservation practice can accommodate such values, and therefore meet local people’s expectations and remain viable in the long term.
- Full Text:
- Date Issued: 2017
- Authors: Cundill, Georgina , Bezerra, Joana C , de Vos, Alta , Ntingana, Nokuthula
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416265 , vital:71334 , xlink:href="https://doi.org/10.1016/j.ecoser.2017.03.011"
- Description: The concept of place attachment can assist to integrate relational values into ecosystem service research, and assist us to rethink the notion of benefits in contemporary protected area thinking. We present a case study from South Africa, where the concept of two-dimensional place attachment was used to understand the relationship between a protected area and a land claimant community that now owns part of this protected area but does not have physical access to the land. A place attachment lens helps refocus access to protected areas as cornerstone to long term sustainability of such areas. Such access must be considered in the context of spatially and economically differentiated users, including a focus on trade-offs between such users. Our findings highlight that when communities previously displaced from protected areas respond to offers of ‘benefit sharing’ with demands for access and recognition as land owners, they are asking for a recognition of relational values, and identity, based on close interaction with nature. A place attachment and relational values perspective raises questions about the extent to which traditional conservation practice can accommodate such values, and therefore meet local people’s expectations and remain viable in the long term.
- Full Text:
- Date Issued: 2017
Biogeographical comparison of the emergent macrophyte, Sagittaria platyphylla in its native and introduced ranges
- Kwong, Raelene M, Sagliocco, Jean L, Harms, Nathan E, Butler, Kym L, Green, Peter T, Martin, Grant D
- Authors: Kwong, Raelene M , Sagliocco, Jean L , Harms, Nathan E , Butler, Kym L , Green, Peter T , Martin, Grant D
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/419287 , vital:71631 , xlink:href="https://doi.org/10.1016/j.aquabot.2017.05.001"
- Description: Understanding why some plant species become invasive is important to predict and prevent future weed threats and identify appropriate management strategies. Many hypotheses have been proposed to explain why plants become invasive, yet few studies have quantitatively compared plant and population parameters between native and introduced range populations to gain an objective perspective on the causes of plant invasion. The present study uses a biogeographical field survey to compare morphological and reproductive traits and abundance between the native range (USA) and two introduced ranges (Australia and South Africa) of Sagittaria platyphylla (Engelm.) J.G. Sm (Alismataceae), a highly invasive freshwater macrophyte. Introduced and native populations differed in sexual reproductive output with the number of achenes per fruiting head and individual achene weight found to be 40% and 50% greater in introduced populations respectively. However, no other morphological traits were found to be consistently different between the native and both introduced ranges, especially after taking into account differences in environmental conditions between the three ranges. Although populations in introduced regions were larger and occupied greater percentage cover, no differences in plant density were evident. Our results suggest that, apart from sexual reproduction, many of the trait patterns observed in S. platyphylla are influenced by environmental and habitat conditions within the native and invaded ranges. We conclude that the enemy release hypothesis best explains the results observed for sexual reproduction. In particular, we hypothesise that a release from natural enemies, specifically a pre-dispersal seed predator, may induce reproductive plasticity in S. platyphylla.
- Full Text:
- Date Issued: 2017
- Authors: Kwong, Raelene M , Sagliocco, Jean L , Harms, Nathan E , Butler, Kym L , Green, Peter T , Martin, Grant D
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/419287 , vital:71631 , xlink:href="https://doi.org/10.1016/j.aquabot.2017.05.001"
- Description: Understanding why some plant species become invasive is important to predict and prevent future weed threats and identify appropriate management strategies. Many hypotheses have been proposed to explain why plants become invasive, yet few studies have quantitatively compared plant and population parameters between native and introduced range populations to gain an objective perspective on the causes of plant invasion. The present study uses a biogeographical field survey to compare morphological and reproductive traits and abundance between the native range (USA) and two introduced ranges (Australia and South Africa) of Sagittaria platyphylla (Engelm.) J.G. Sm (Alismataceae), a highly invasive freshwater macrophyte. Introduced and native populations differed in sexual reproductive output with the number of achenes per fruiting head and individual achene weight found to be 40% and 50% greater in introduced populations respectively. However, no other morphological traits were found to be consistently different between the native and both introduced ranges, especially after taking into account differences in environmental conditions between the three ranges. Although populations in introduced regions were larger and occupied greater percentage cover, no differences in plant density were evident. Our results suggest that, apart from sexual reproduction, many of the trait patterns observed in S. platyphylla are influenced by environmental and habitat conditions within the native and invaded ranges. We conclude that the enemy release hypothesis best explains the results observed for sexual reproduction. In particular, we hypothesise that a release from natural enemies, specifically a pre-dispersal seed predator, may induce reproductive plasticity in S. platyphylla.
- Full Text:
- Date Issued: 2017
Borneol-triarylcorrole hybrids with chiral-optical response and anticancer behaviours
- Fu, Bo, Wang, Lin, Yu, Xiaoxiao, Fang, Xianying, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Liang, Xu, Xu, Haijun
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
Bushmeat use is widespread but under-researched in rural communities of South Africa
- Martins, Vusumzi, Shackleton, Charlie M
- Authors: Martins, Vusumzi , Shackleton, Charlie M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/179745 , vital:43167 , xlink:href="https://doi.org/10.1016/j.gecco.2019.e00583"
- Description: Bushmeat hunting and consumption is common throughout sub-Saharan Africa. Yet, a recent review indicated that the prevalence and nature of bushmeat hunting was little researched or understood in southern African savannas. Here we present information from a number of rural livelihoods studies in South Africa that indicate that bushmeat consumption is common, with typically between 30 and 60% of rural households in the communal tenure regions stating that they consume it. Yet there are only five studies in the country explicitly investigating bushmeat hunting practices, motivations, offtake and target species. A review of the five studies indicates that bushmeat hunting is largely a male activity and that motivations and practices vary between sites. Hunting with dogs is the most common method, targeting multiple small and medium-sized species. With such widespread consumption, it is possible that bushmeat hunting may have significant effects on the population status of some target species and consequently requires urgent and in-depth research of both practices and effects
- Full Text:
- Date Issued: 2019
- Authors: Martins, Vusumzi , Shackleton, Charlie M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/179745 , vital:43167 , xlink:href="https://doi.org/10.1016/j.gecco.2019.e00583"
- Description: Bushmeat hunting and consumption is common throughout sub-Saharan Africa. Yet, a recent review indicated that the prevalence and nature of bushmeat hunting was little researched or understood in southern African savannas. Here we present information from a number of rural livelihoods studies in South Africa that indicate that bushmeat consumption is common, with typically between 30 and 60% of rural households in the communal tenure regions stating that they consume it. Yet there are only five studies in the country explicitly investigating bushmeat hunting practices, motivations, offtake and target species. A review of the five studies indicates that bushmeat hunting is largely a male activity and that motivations and practices vary between sites. Hunting with dogs is the most common method, targeting multiple small and medium-sized species. With such widespread consumption, it is possible that bushmeat hunting may have significant effects on the population status of some target species and consequently requires urgent and in-depth research of both practices and effects
- Full Text:
- Date Issued: 2019
Can local use assist in controlling invasive alien species in tropical forests?: The case of Lantana camara in southern India
- Kannan, Ramesh, Shackleton, Charlie M, Krishnan, Smitha, Shaanker, Ramanan U
- Authors: Kannan, Ramesh , Shackleton, Charlie M , Krishnan, Smitha , Shaanker, Ramanan U
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180423 , vital:43387 , xlink:href="https://doi.org/10.1016/j.foreco.2016.06.016"
- Description: Many invasive alien species (IAS) are used by local communities for a variety of subsistence and income generating purposes. This frequently poses a conflict of interest for their removal due to forest conservation and biodiversity concerns. However, if local use can simultaneously check or control specific IAS, the conflict can be avoided and both development and forest conservation perspectives accommodated in the short to medium term. We examine this for Lantana camara invasion in southern India through assessment of the demand for and impacts of harvesting on this globally problematic IAS. We interviewed local artisans regarding their knowledge and quantities of Lantana used, along with forest surveys to estimate Lantana densities and size classes in harvested and unharvested sites, and lastly we undertook controlled cutting in moist and dry deciduous forests in both the wet and dry seasons to examine rate of regrowth and mortality. Over the entire study area the abundance of Lantana far outweighed local demand, but at small scales around villages, density and size classes were significantly reduced through harvesting. The controlled cutting experiment showed marked seasonal differences, with the most severe cutting intensity resulting in significant mortality when Lantana plants were cut in the wet season, but with limited effect when cut in the dry season. We conclude that promoting local use of IAS may be a feasible approach in controlling them and thereby limiting their impacts in forests.
- Full Text:
- Date Issued: 2016
- Authors: Kannan, Ramesh , Shackleton, Charlie M , Krishnan, Smitha , Shaanker, Ramanan U
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180423 , vital:43387 , xlink:href="https://doi.org/10.1016/j.foreco.2016.06.016"
- Description: Many invasive alien species (IAS) are used by local communities for a variety of subsistence and income generating purposes. This frequently poses a conflict of interest for their removal due to forest conservation and biodiversity concerns. However, if local use can simultaneously check or control specific IAS, the conflict can be avoided and both development and forest conservation perspectives accommodated in the short to medium term. We examine this for Lantana camara invasion in southern India through assessment of the demand for and impacts of harvesting on this globally problematic IAS. We interviewed local artisans regarding their knowledge and quantities of Lantana used, along with forest surveys to estimate Lantana densities and size classes in harvested and unharvested sites, and lastly we undertook controlled cutting in moist and dry deciduous forests in both the wet and dry seasons to examine rate of regrowth and mortality. Over the entire study area the abundance of Lantana far outweighed local demand, but at small scales around villages, density and size classes were significantly reduced through harvesting. The controlled cutting experiment showed marked seasonal differences, with the most severe cutting intensity resulting in significant mortality when Lantana plants were cut in the wet season, but with limited effect when cut in the dry season. We conclude that promoting local use of IAS may be a feasible approach in controlling them and thereby limiting their impacts in forests.
- Full Text:
- Date Issued: 2016
Catalytic activity of iron and cobalt phthalocyanine complexes towards the oxidation of cyclohexene using tert-butylhydroperoxide and chloroperoxybenzoic acid
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
Catalytic oxidation of thioanisole using oxovanadium (IV)‐functionalized electrospun polybenzimidazole nanofibers
- Walmsley, Ryan S, Hlangothi, Percy, Litwinski, Christian, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Walmsley, Ryan S , Hlangothi, Percy , Litwinski, Christian , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242083 , vital:51000 , xlink:href="https://doi.org/10.1002/app.38067"
- Description: Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)-functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo-continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh−1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts.
- Full Text:
- Date Issued: 2013
- Authors: Walmsley, Ryan S , Hlangothi, Percy , Litwinski, Christian , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242083 , vital:51000 , xlink:href="https://doi.org/10.1002/app.38067"
- Description: Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)-functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo-continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh−1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts.
- Full Text:
- Date Issued: 2013
CdTe quantum dots functionalized with 4-amino-2, 2, 6, 6-tetramethylpiperidine-N-oxide as luminescent nanoprobe for the sensitive recognition of bromide ion
- Adegoke, Oluwasesan, Hosten, Eric C, McCleland, Cedric, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244393 , vital:51253 , xlink:href="https://doi.org/10.1016/j.aca.2012.01.040"
- Description: A novel bromide ion-selective modified nanoprobe sensor based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT)-functionalized CdTe quantum dots (QDs-4AT) has been developed. Fluorescence quenching of the QDs by 4AT was observed. The functionalized QDs-4AT nanoprobe allowed a highly sensitive determination of bromide ion via analyte-induced change in the photoluminescence (fluorescence recovery) of the modified QDs. A detection limit of 0.6 nM of bromide ion was obtained, while the interfering effect of other inorganic cations and anions was investigated to examine the selectivity of the nanoprobe. The linear range was between 0.01 and 0.13 μM. Combined fluorescence lifetime and electron paramagnetic resonance measurements confirmed electron transfer processes between bromide ion and QDs-4AT.
- Full Text:
- Date Issued: 2012
- Authors: Adegoke, Oluwasesan , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244393 , vital:51253 , xlink:href="https://doi.org/10.1016/j.aca.2012.01.040"
- Description: A novel bromide ion-selective modified nanoprobe sensor based on 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4AT)-functionalized CdTe quantum dots (QDs-4AT) has been developed. Fluorescence quenching of the QDs by 4AT was observed. The functionalized QDs-4AT nanoprobe allowed a highly sensitive determination of bromide ion via analyte-induced change in the photoluminescence (fluorescence recovery) of the modified QDs. A detection limit of 0.6 nM of bromide ion was obtained, while the interfering effect of other inorganic cations and anions was investigated to examine the selectivity of the nanoprobe. The linear range was between 0.01 and 0.13 μM. Combined fluorescence lifetime and electron paramagnetic resonance measurements confirmed electron transfer processes between bromide ion and QDs-4AT.
- Full Text:
- Date Issued: 2012
Characterising the shared genetic influences between schizophrenia and subcortical brain regions
- Wooton, Olivia, Campbell, Megan M, Jahanshad, Neda, Thompson, Paul, Stein, Dan J, Dalvie, Shareefa
- Authors: Wooton, Olivia , Campbell, Megan M , Jahanshad, Neda , Thompson, Paul , Stein, Dan J , Dalvie, Shareefa
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/302450 , vital:58197 , xlink:href="https://doi.org/10.1016/j.euroneuro.2022.07.533"
- Description: Background: Abnormalities in brain structural volumes are well established in schizophrenia (SZ) and have been proposed as an endophenotype for the disorder. Despite increasing interest in the genetic relationship between brain structural volumes and SZ, our knowledge of the genetic overlap between the phenotypes is limited. This study aims to extend our current understanding of the shared genetic influences between SZ and subcortical brain volumes using data from the latest genome-wide association studies for the respective phenotypes (GWAS) and novel statistical approaches. Additionally, we will explore whether the association between schizophrenia and abnormal regional brain volumes is causal in nature. Methods: Summary statistics were obtained from the largest Psychiatric Genomic Consortium (PGC)-SZ GWAS (Ncase = 69,369, Ncontrol = 236,642) and the CHARGEENIGMA-UKBB GWAS of volumetric measures for eight subcortical brain regions (the nucleus accumbens, amygdala, brainstem, caudate nucleus, hippocampus, globus pallidus, putamen, and thalamus), and total intracranial volume (N = 30,983 - 40,380). Single nucleotide polymorphism (SNP) effect concordance analysis (SECA) was used to assess pleiotropy and concordance. Genetic correlation was assessed using linkage disequilibrium score regression (LDSR) and the pleiotropy informed conditional FDR approach was applied to identify SNPs associated with SZ conditional on their association with subcortical brain volumes. Mendelian randomization (MR) was used to test for causal association between SZ and each brain region. Results: There was evidence of global pleiotropy between SZ, and all examined subcortical brain regions. Inverse concordance between the genetic determinants of SZ and volumes of the nucleus accumbens, amygdala, brainstem, hippocampus, and thalamus was observed. Increased statistical power to detect SZ risk loci was shown when conditioning on subcortical brain volumes. There was no significant evidence for a causal effect of any of the examined brain regions on schizophrenia risk. Discussion: These data confirm the shared genetic basis of SZ and specific intracranial and subcortical brain volumes and provide evidence for negative concordance between SZ and volumes of the nucleus accumbens, amygdala, brainstem, hippocampus, and thalamus. Leveraging the genetic overlap between SZ and subcortical brain volumes has the potential to provide novel insights into the biological basis of the disorder.
- Full Text:
- Date Issued: 2022
- Authors: Wooton, Olivia , Campbell, Megan M , Jahanshad, Neda , Thompson, Paul , Stein, Dan J , Dalvie, Shareefa
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/302450 , vital:58197 , xlink:href="https://doi.org/10.1016/j.euroneuro.2022.07.533"
- Description: Background: Abnormalities in brain structural volumes are well established in schizophrenia (SZ) and have been proposed as an endophenotype for the disorder. Despite increasing interest in the genetic relationship between brain structural volumes and SZ, our knowledge of the genetic overlap between the phenotypes is limited. This study aims to extend our current understanding of the shared genetic influences between SZ and subcortical brain volumes using data from the latest genome-wide association studies for the respective phenotypes (GWAS) and novel statistical approaches. Additionally, we will explore whether the association between schizophrenia and abnormal regional brain volumes is causal in nature. Methods: Summary statistics were obtained from the largest Psychiatric Genomic Consortium (PGC)-SZ GWAS (Ncase = 69,369, Ncontrol = 236,642) and the CHARGEENIGMA-UKBB GWAS of volumetric measures for eight subcortical brain regions (the nucleus accumbens, amygdala, brainstem, caudate nucleus, hippocampus, globus pallidus, putamen, and thalamus), and total intracranial volume (N = 30,983 - 40,380). Single nucleotide polymorphism (SNP) effect concordance analysis (SECA) was used to assess pleiotropy and concordance. Genetic correlation was assessed using linkage disequilibrium score regression (LDSR) and the pleiotropy informed conditional FDR approach was applied to identify SNPs associated with SZ conditional on their association with subcortical brain volumes. Mendelian randomization (MR) was used to test for causal association between SZ and each brain region. Results: There was evidence of global pleiotropy between SZ, and all examined subcortical brain regions. Inverse concordance between the genetic determinants of SZ and volumes of the nucleus accumbens, amygdala, brainstem, hippocampus, and thalamus was observed. Increased statistical power to detect SZ risk loci was shown when conditioning on subcortical brain volumes. There was no significant evidence for a causal effect of any of the examined brain regions on schizophrenia risk. Discussion: These data confirm the shared genetic basis of SZ and specific intracranial and subcortical brain volumes and provide evidence for negative concordance between SZ and volumes of the nucleus accumbens, amygdala, brainstem, hippocampus, and thalamus. Leveraging the genetic overlap between SZ and subcortical brain volumes has the potential to provide novel insights into the biological basis of the disorder.
- Full Text:
- Date Issued: 2022
Characterization and electrocatalytic behaviour of glassy carbon electrode modified with nickel nanoparticles towards amitrole detection
- Maringa, Audacity, Mugadza, Tawanda, Antunes, Edith M, Nyokong, Tebello
- Authors: Maringa, Audacity , Mugadza, Tawanda , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241793 , vital:50970 , xlink:href="https://doi.org/10.1016/j.jelechem.2013.04.022"
- Description: We report on the synthesis of Ni nanoparticles (NiNPs) and their application in electrocatalysis in comparison with nickel phthalocyanine (NiPc). UV–vis spectroscopy, powder X-ray diffraction, transmission electron microscopy and electron paramagnetic resonance were used in the characterization of NiNPs. Cyclic voltammetry and electrochemical impedance spectroscopy were used in electrocatalytic studies of amitrole on the glassy carbon electrode modified with NiNPs. The apparent and catalytic rate constants for amitrole on the NiNP-GCE were found to be 2.58 × 10−5 cm s−1 and 1.11 × 103 M−1 s−1, respectively.
- Full Text:
- Date Issued: 2013
- Authors: Maringa, Audacity , Mugadza, Tawanda , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241793 , vital:50970 , xlink:href="https://doi.org/10.1016/j.jelechem.2013.04.022"
- Description: We report on the synthesis of Ni nanoparticles (NiNPs) and their application in electrocatalysis in comparison with nickel phthalocyanine (NiPc). UV–vis spectroscopy, powder X-ray diffraction, transmission electron microscopy and electron paramagnetic resonance were used in the characterization of NiNPs. Cyclic voltammetry and electrochemical impedance spectroscopy were used in electrocatalytic studies of amitrole on the glassy carbon electrode modified with NiNPs. The apparent and catalytic rate constants for amitrole on the NiNP-GCE were found to be 2.58 × 10−5 cm s−1 and 1.11 × 103 M−1 s−1, respectively.
- Full Text:
- Date Issued: 2013
Characterization and photophysical behavior of phthalocyanines when grafted onto silica nanoparticles
- Fashina, Adedayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241981 , vital:50989 , xlink:href="https://doi.org/10.1016/j.poly.2013.01.037"
- Description: This work reports on the functionalization of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally with 4-carboxyphenoxyl and 3-carboxyphenoxyl groups. The phthalocyanine dyes have a free carboxyl group, facilitating the covalent attachment of the dyes on the silica surface via amide bond formation. The phthalocyanine functionalized silica nanoparticles showed higher fluorescence and triplet quantum yields as well as longer triplet lifetimes compared to the free phthalocyanines.
- Full Text:
- Date Issued: 2013
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241981 , vital:50989 , xlink:href="https://doi.org/10.1016/j.poly.2013.01.037"
- Description: This work reports on the functionalization of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally with 4-carboxyphenoxyl and 3-carboxyphenoxyl groups. The phthalocyanine dyes have a free carboxyl group, facilitating the covalent attachment of the dyes on the silica surface via amide bond formation. The phthalocyanine functionalized silica nanoparticles showed higher fluorescence and triplet quantum yields as well as longer triplet lifetimes compared to the free phthalocyanines.
- Full Text:
- Date Issued: 2013
Characterization of 2,(3)-tetra-(4-oxo-benzamide) phthalocyaninato cobalt (II)—single walled carbon nanotube conjugate platforms and their use in electrocatalysis of amitrole
- Mugadza, Tawanda, Arslanoğlu, Yasin, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244382 , vital:51252 , xlink:href="https://doi.org/10.1016/j.electacta.2012.02.041"
- Description: In this paper we report on the use of carboxylic acid functionalized single walled carbon nanotubes (SWCNT) in the synthesis of 2,(3)-tetra-(4-oxo-benzamide)phthalocyaninato cobalt (II)–single walled carbon nanotube conjugates (CoTOBPc–SWCNT), their characterization and application in the electrocatalytic oxidation of amitrole. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were used for the detection of amitrole on the modified glassy carbon electrode. The catalytic rate constant was 1.6 × 103 M−1 s−1 and the apparent electron rate transfer constant was 1.5 × 10−5 cm s−1. The linear dynamic range was 1.0 × 10−6–3.0 × 10−5 M, with a sensitivity of ∼1.13 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2012
- Authors: Mugadza, Tawanda , Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244382 , vital:51252 , xlink:href="https://doi.org/10.1016/j.electacta.2012.02.041"
- Description: In this paper we report on the use of carboxylic acid functionalized single walled carbon nanotubes (SWCNT) in the synthesis of 2,(3)-tetra-(4-oxo-benzamide)phthalocyaninato cobalt (II)–single walled carbon nanotube conjugates (CoTOBPc–SWCNT), their characterization and application in the electrocatalytic oxidation of amitrole. Cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy were used for the detection of amitrole on the modified glassy carbon electrode. The catalytic rate constant was 1.6 × 103 M−1 s−1 and the apparent electron rate transfer constant was 1.5 × 10−5 cm s−1. The linear dynamic range was 1.0 × 10−6–3.0 × 10−5 M, with a sensitivity of ∼1.13 A mol−1 L cm−2.
- Full Text:
- Date Issued: 2012
Characterization of conjugates of NaYF4
- Watkins, Zane, Uddin, Imran, Britton, Jonathan, Nyokong, Tebello
- Authors: Watkins, Zane , Uddin, Imran , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238132 , vital:50589 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.10.011"
- Description: NaYF4:Er/Yb/Gd upconversion nanoparticles (UCNP) capped with amino groups were covalently attached to chloro aluminium tetrasulphonated phthalocyanine (ClAlTSPc) and chloro aluminium tetracarboxy phthalocyanine (ClAlTCPc). The conjugates were characterized using different techniques such as infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). There was a decrease in the intensity of fluorescence emission spectra of the UCNPs at 658 nm in the presence of the phthalocyanines. This decrease indicates an energy transfer between the donor UCNP and conjugated accepting phthalocyanine (Pc), due to Förster resonance energy transfer (FRET). FRET efficiencies of 18% and 21% for ClAlTSPc and ClAlTCPc, respectively, were obtained. Oxygen generation by ClAlTSPc following FRET was proved.
- Full Text:
- Date Issued: 2017
- Authors: Watkins, Zane , Uddin, Imran , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238132 , vital:50589 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.10.011"
- Description: NaYF4:Er/Yb/Gd upconversion nanoparticles (UCNP) capped with amino groups were covalently attached to chloro aluminium tetrasulphonated phthalocyanine (ClAlTSPc) and chloro aluminium tetracarboxy phthalocyanine (ClAlTCPc). The conjugates were characterized using different techniques such as infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). There was a decrease in the intensity of fluorescence emission spectra of the UCNPs at 658 nm in the presence of the phthalocyanines. This decrease indicates an energy transfer between the donor UCNP and conjugated accepting phthalocyanine (Pc), due to Förster resonance energy transfer (FRET). FRET efficiencies of 18% and 21% for ClAlTSPc and ClAlTCPc, respectively, were obtained. Oxygen generation by ClAlTSPc following FRET was proved.
- Full Text:
- Date Issued: 2017
Characterization of electrodes modified by one pot or step by step electro-click reaction and axial ligation of iron tetracarboxyphthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193892 , vital:45403 , xlink:href="https://doi.org/10.1016/j.electacta.2014.09.011"
- Description: The modification of the glassy carbon electrode (GCE) was carried out using two methods. The first method is simultaneous electropolymerization and electro-click followed by immersion into a solution of dimethyl formamide (DMF) containing FeTCPc. The second method is step by step whereby electropolymerization is carried out first followed by electro-click and then immersion into a DMF solution containing FeTCPc. From the electrochemical characterization, it was observed that the second route (step by step method) was the best as indicated by the ferricyanide studies (cyclic voltammetry and scanning electrochemical microscopy). In the electrooxidation of hydrazine, we obtained a potential of 0.26 V. Of interest were the detection limit of 6.4 μM and the catalytic rate constant of 2.1 × 109 cm3 mol−1 s−1. This shows that the sensor can be used for the electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2014
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193892 , vital:45403 , xlink:href="https://doi.org/10.1016/j.electacta.2014.09.011"
- Description: The modification of the glassy carbon electrode (GCE) was carried out using two methods. The first method is simultaneous electropolymerization and electro-click followed by immersion into a solution of dimethyl formamide (DMF) containing FeTCPc. The second method is step by step whereby electropolymerization is carried out first followed by electro-click and then immersion into a DMF solution containing FeTCPc. From the electrochemical characterization, it was observed that the second route (step by step method) was the best as indicated by the ferricyanide studies (cyclic voltammetry and scanning electrochemical microscopy). In the electrooxidation of hydrazine, we obtained a potential of 0.26 V. Of interest were the detection limit of 6.4 μM and the catalytic rate constant of 2.1 × 109 cm3 mol−1 s−1. This shows that the sensor can be used for the electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2014
Characterization of glassy carbon electrodes modified with carbon nanotubes and iron phthalocyanine through grafting and click chemistry
- Coates, Megan, Nyokong, Tebello
- Authors: Coates, Megan , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193746 , vital:45392 , xlink:href="https://doi.org/10.1016/j.electacta.2012.12.112"
- Description: A glassy carbon electrode was modified by adsorption of single-walled carbon nanotubes, followed by electrochemical grafting of 4-azidobenzenediazonium salt, which was in turn reacted with ethynylpyridine through the Sharpless “click chemistry” reaction. Thereafter, iron phthalocyanine was attached to the electrode through axial ligation to the pyridine group. The modified electrode was characterised using X-ray photoelectron spectroscopy and scanning electrochemical microscopy, and well as electrochemistry. The electrocatalytic ability of the modified electrode was tested using hydrazine as a sample analyte, and showed a significant 10-fold improvement in the detection of hydrazine compared to the surface without nanotubes, and comparable stability. The linear range for this surface was over 1.0 × 10−5 to 1.0 × 10−4 mol dm−3, with a limit of detection of 1.10 ± 0.06 μmol dm−3 and sensitivity of 15.61 μA mM−1.
- Full Text:
- Date Issued: 2013
- Authors: Coates, Megan , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193746 , vital:45392 , xlink:href="https://doi.org/10.1016/j.electacta.2012.12.112"
- Description: A glassy carbon electrode was modified by adsorption of single-walled carbon nanotubes, followed by electrochemical grafting of 4-azidobenzenediazonium salt, which was in turn reacted with ethynylpyridine through the Sharpless “click chemistry” reaction. Thereafter, iron phthalocyanine was attached to the electrode through axial ligation to the pyridine group. The modified electrode was characterised using X-ray photoelectron spectroscopy and scanning electrochemical microscopy, and well as electrochemistry. The electrocatalytic ability of the modified electrode was tested using hydrazine as a sample analyte, and showed a significant 10-fold improvement in the detection of hydrazine compared to the surface without nanotubes, and comparable stability. The linear range for this surface was over 1.0 × 10−5 to 1.0 × 10−4 mol dm−3, with a limit of detection of 1.10 ± 0.06 μmol dm−3 and sensitivity of 15.61 μA mM−1.
- Full Text:
- Date Issued: 2013
Characterization of manganese tetraarylthiosubstituted phthalocyanines self assembled monolayers
- Matemadombo, Fungisai, Durmus, Mahmut, Togo, Chamunorwa, Limson, Janice L, Nyokong, Tebello
- Authors: Matemadombo, Fungisai , Durmus, Mahmut , Togo, Chamunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263364 , vital:53621 , xlink:href="https://doi.org/10.1016/j.electacta.2009.04.059"
- Description: Manganese tetraarylthiosubstituted phthalocyanines (complexes 1–5) have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. SAM characteristics reported in this work are: ion barrier factor (∼1); interfacial capacitance (303–539 μF cm−2) and surface coverage (1.06 × 10−10–2.80 × 10−10 mol cm−2). Atomic force microscopy was employed in characterizing a SAM. SAMs of complexes 1–5 were employed to detect L-cysteine (with limit of detection ranging from 2.83 × 10−7 to 3.14 × 10−7 M at potentials of 0.68–0.75 V vs. Ag|AgCl) and nitrite (limit of detection ranging from 1.78 × 10−7 to 3.02 × 10−7 M at potentials of 0.69–0.76 V vs. Ag|AgCl).
- Full Text:
- Date Issued: 2009
- Authors: Matemadombo, Fungisai , Durmus, Mahmut , Togo, Chamunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263364 , vital:53621 , xlink:href="https://doi.org/10.1016/j.electacta.2009.04.059"
- Description: Manganese tetraarylthiosubstituted phthalocyanines (complexes 1–5) have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. SAM characteristics reported in this work are: ion barrier factor (∼1); interfacial capacitance (303–539 μF cm−2) and surface coverage (1.06 × 10−10–2.80 × 10−10 mol cm−2). Atomic force microscopy was employed in characterizing a SAM. SAMs of complexes 1–5 were employed to detect L-cysteine (with limit of detection ranging from 2.83 × 10−7 to 3.14 × 10−7 M at potentials of 0.68–0.75 V vs. Ag|AgCl) and nitrite (limit of detection ranging from 1.78 × 10−7 to 3.02 × 10−7 M at potentials of 0.69–0.76 V vs. Ag|AgCl).
- Full Text:
- Date Issued: 2009
Characterization of nickel tetrahydroxy phthalocyanine complexes and the electrocatalytic oxidation of 4-chlorophenol
- Khene, Samson M, Lobb, Kevin A, Nyokong, Tebello
- Authors: Khene, Samson M , Lobb, Kevin A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263308 , vital:53616 , xlink:href="https://doi.org/10.1016/j.ica.2009.08.019"
- Description: This work reports on the use of nickel(II) tetrahydroxy (NiPc(OH)4) and (poly-Ni(OH)Pc(OH)4) phthalocyanine complexes as films on ordinary poly graphite electrode (OPGE) for the electrochemical oxidation of 4-chlorophenol (4-CP). The NiPc(OH)4 film was electrotransformed to Ni(OH)Pc(OH)4 film in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridge form. The result showed that the Ni(OH)Pc(OH)4 film on OPGE was more electroactive in terms of increase in current and less catalytic in terms of potential compared to the adsorbed NiPc(OH)4 on OPGE. The reactivity of the two molecules was explained by theoretical calculations. The energies of the frontier orbitals of NiPc(OH)4, Ni(OH)Pc(OH)4 and 4-chlorophenol were calculated using density functional theory (DFT) method. The inter molecular hardness (η) and donor–acceptor hardness (ηDA) of Ni(OH)Pc(OH)4, NiPc(OH)4, Ni(OH)Pc(OH)4/4-chlorophenol and NiPc(OH)4/4-chlorophenol were estimated. The Ni(OH)Pc(OH)4, showed stronger interaction with 4-chlorophenol than NiPc(OH)4. DFT method was also used to model IR and Raman spectrum of H2Pc(OH)4 and NiPc(OH)4.
- Full Text:
- Date Issued: 2009
- Authors: Khene, Samson M , Lobb, Kevin A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263308 , vital:53616 , xlink:href="https://doi.org/10.1016/j.ica.2009.08.019"
- Description: This work reports on the use of nickel(II) tetrahydroxy (NiPc(OH)4) and (poly-Ni(OH)Pc(OH)4) phthalocyanine complexes as films on ordinary poly graphite electrode (OPGE) for the electrochemical oxidation of 4-chlorophenol (4-CP). The NiPc(OH)4 film was electrotransformed to Ni(OH)Pc(OH)4 film in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridge form. The result showed that the Ni(OH)Pc(OH)4 film on OPGE was more electroactive in terms of increase in current and less catalytic in terms of potential compared to the adsorbed NiPc(OH)4 on OPGE. The reactivity of the two molecules was explained by theoretical calculations. The energies of the frontier orbitals of NiPc(OH)4, Ni(OH)Pc(OH)4 and 4-chlorophenol were calculated using density functional theory (DFT) method. The inter molecular hardness (η) and donor–acceptor hardness (ηDA) of Ni(OH)Pc(OH)4, NiPc(OH)4, Ni(OH)Pc(OH)4/4-chlorophenol and NiPc(OH)4/4-chlorophenol were estimated. The Ni(OH)Pc(OH)4, showed stronger interaction with 4-chlorophenol than NiPc(OH)4. DFT method was also used to model IR and Raman spectrum of H2Pc(OH)4 and NiPc(OH)4.
- Full Text:
- Date Issued: 2009
Characterization of polymeric film of a new manganese phthalocyanine complex octa-substituted with 2-diethylaminoethanethiol, and its use for the electrochemical detection of bentazon
- Akinbulu, Isaac A, Nyokong, Tebello
- Authors: Akinbulu, Isaac A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262568 , vital:53534 , xlink:href="https://doi.org/10.1016/j.electacta.2009.07.074"
- Description: Manganese acetate octakis-(2-diethyaminoethanethiol) phthalocyanine (AcMnODEAETPc) was newly synthesized and characterized by spectroscopic and electrochemical methods. Solution electrochemistry of the complex showed three redox processes assigned to MnIIIPc−1/MnIIIPc−2, MnIIIPc−2/MnIIPc−2 and MnIIPc−2/MnIIPc−3 species. The new molecule was polymerized onto a glassy carbon electrode (GCE) to form thin films of different thickness, giving poly-10-AcMnODEAETPc-GCE, poly-20-AcMnODEAETPc-GCE and poly-30-AcMnODEAETPc-GCE, where 10, 20 and 30 represent the number of voltammetry scans during polymerization. Three distinct redox processes were observed on the modified electrode in 0.1 M phosphate buffer solution, pH 5, which confirmed the formation of the polymer. The current signal due to the herbicide, bentazon, was dependent on film thickness; the best signal was obtained on poly-20-AcMnODEAETPc-GCE while poly-10-AcMnODEAETPc-GCE gave the least signal. However, the signals due to the herbicide were better on the different films compared to the bare electrode. Electrochemical impedance spectroscopy (EIS) technique revealed that differences in film thickness offered different charge transfer resistances, Rct, hence difference in current signals for bentazon oxidation were observed on these films. A Tafel slope of 77 mV/decade, obtained for the herbicide on poly-20-AcMnODEAETPc-GCE, denotes a fast one electron transfer followed by a slow chemical step in the electro-oxidation of bentazon. The voltammetry signals of the herbicide on the films indicated the likely involvement of ring-based redox processes in the detection of the herbicide. A plot of background corrected current response, on this film, versus the concentration of bentazon was linear within the range 50–750 μM with a detection limit of 2.48 × 10−7 M.
- Full Text:
- Date Issued: 2009
- Authors: Akinbulu, Isaac A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262568 , vital:53534 , xlink:href="https://doi.org/10.1016/j.electacta.2009.07.074"
- Description: Manganese acetate octakis-(2-diethyaminoethanethiol) phthalocyanine (AcMnODEAETPc) was newly synthesized and characterized by spectroscopic and electrochemical methods. Solution electrochemistry of the complex showed three redox processes assigned to MnIIIPc−1/MnIIIPc−2, MnIIIPc−2/MnIIPc−2 and MnIIPc−2/MnIIPc−3 species. The new molecule was polymerized onto a glassy carbon electrode (GCE) to form thin films of different thickness, giving poly-10-AcMnODEAETPc-GCE, poly-20-AcMnODEAETPc-GCE and poly-30-AcMnODEAETPc-GCE, where 10, 20 and 30 represent the number of voltammetry scans during polymerization. Three distinct redox processes were observed on the modified electrode in 0.1 M phosphate buffer solution, pH 5, which confirmed the formation of the polymer. The current signal due to the herbicide, bentazon, was dependent on film thickness; the best signal was obtained on poly-20-AcMnODEAETPc-GCE while poly-10-AcMnODEAETPc-GCE gave the least signal. However, the signals due to the herbicide were better on the different films compared to the bare electrode. Electrochemical impedance spectroscopy (EIS) technique revealed that differences in film thickness offered different charge transfer resistances, Rct, hence difference in current signals for bentazon oxidation were observed on these films. A Tafel slope of 77 mV/decade, obtained for the herbicide on poly-20-AcMnODEAETPc-GCE, denotes a fast one electron transfer followed by a slow chemical step in the electro-oxidation of bentazon. The voltammetry signals of the herbicide on the films indicated the likely involvement of ring-based redox processes in the detection of the herbicide. A plot of background corrected current response, on this film, versus the concentration of bentazon was linear within the range 50–750 μM with a detection limit of 2.48 × 10−7 M.
- Full Text:
- Date Issued: 2009