Fluorescence behaviour of supramolecular hybrids containing graphene quantum dots and pyrene-derivatized phthalocyanines and porphyrins
- Achadu, Ojodomo John, Managa, Muthumuni, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
- Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
- Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
- Full Text:
- Date Issued: 2017
Graphene quantum dots decorated with maleimide and zinc tetramaleimido-phthalocyanine: Application in the design of “OFF-ON” fluorescence sensors for biothiols
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188282 , vital:44741 , xlink:href="https://doi.org/10.1016/j.talanta.2017.01.031"
- Description: The fabrication of maleimide-derivatized graphene quantum dots (M-GQDs) and zinc phthalocyanine (2) as novel sensor probes for the selective detection of biothiols (cysteine, homocysteine or glutathione) through the rapid and specific Michael addition reaction between biothiols and the maleimide-derivatized probes is presented in this study. GQDs directly functionalized with maleimide units (M-GQDs) were synthesized and deployed for biothiols recognition following the principle of Michael addition. M-GQDs probe was found to be highly sensitive and selective towards biothiols detection in the nanomolar range in aqueous solution and at physiological pH (7.0). On the other hand, non-covalent interaction between pristine GQDs and novel zinc tetramaleimido-derivatized phthalocyanine resulted in the quenching of the pristine GQDs fluorescence emission which was switched back to the “ON” mode by Michael addition mechanism in the presence of biothiols. Tested relevant biomolecules did not interfere in the quantitative recognition of the biothiols. The probes showed to be highly sensitive, specific and selective for biothiols sensing in simulated real samples.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188282 , vital:44741 , xlink:href="https://doi.org/10.1016/j.talanta.2017.01.031"
- Description: The fabrication of maleimide-derivatized graphene quantum dots (M-GQDs) and zinc phthalocyanine (2) as novel sensor probes for the selective detection of biothiols (cysteine, homocysteine or glutathione) through the rapid and specific Michael addition reaction between biothiols and the maleimide-derivatized probes is presented in this study. GQDs directly functionalized with maleimide units (M-GQDs) were synthesized and deployed for biothiols recognition following the principle of Michael addition. M-GQDs probe was found to be highly sensitive and selective towards biothiols detection in the nanomolar range in aqueous solution and at physiological pH (7.0). On the other hand, non-covalent interaction between pristine GQDs and novel zinc tetramaleimido-derivatized phthalocyanine resulted in the quenching of the pristine GQDs fluorescence emission which was switched back to the “ON” mode by Michael addition mechanism in the presence of biothiols. Tested relevant biomolecules did not interfere in the quantitative recognition of the biothiols. The probes showed to be highly sensitive, specific and selective for biothiols sensing in simulated real samples.
- Full Text:
- Date Issued: 2017
Graphene quantum dots coordinated to mercaptopyridine-substituted phthalocyanines: Characterization and application as fluorescence “turn ON” nanoprobes
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188293 , vital:44742 , xlink:href="https://doi.org/10.1016/j.saa.2016.11.043"
- Description: This study reports on the design of novel nanoconjugates of graphene quantum dots (GQDs) and tetra or octa-mercaptopyridine-substituted zinc and aluminium phthalocyanines (Pcs) deployed as fluorescence “turn ON” nanoprobes. The phthalocyanines were separately adsorbed onto the planar structure of graphene quantum dots (GQDs) via π-π stacking interaction to form GQDs-mercaptopyridine Pcs nanoconjugates. The quaternized Pc complexes could also interact with the GQDs through electrostatic attraction due to the positive charges on the Pcs ring substituents and the negative charges on the surface of GQDs. The fluorescence emission of the GQDs was quenched upon coordination to the respective Pcs. However, the fluorescence emission was “turned ON” in the presence of Hg2 + employed as a test analyte. The mechanism of the “turn ON” of the GQDs emission in the nanoconjugates is ascribed to the strong affinity of Hg2 + to bind with the bridging sulfur on the Pcs periphery thereby disrupting the π-π stacking interaction between the GQDs and the Pcs with a consequent “turn ON” of the coordinated GQDs' fluorescence.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188293 , vital:44742 , xlink:href="https://doi.org/10.1016/j.saa.2016.11.043"
- Description: This study reports on the design of novel nanoconjugates of graphene quantum dots (GQDs) and tetra or octa-mercaptopyridine-substituted zinc and aluminium phthalocyanines (Pcs) deployed as fluorescence “turn ON” nanoprobes. The phthalocyanines were separately adsorbed onto the planar structure of graphene quantum dots (GQDs) via π-π stacking interaction to form GQDs-mercaptopyridine Pcs nanoconjugates. The quaternized Pc complexes could also interact with the GQDs through electrostatic attraction due to the positive charges on the Pcs ring substituents and the negative charges on the surface of GQDs. The fluorescence emission of the GQDs was quenched upon coordination to the respective Pcs. However, the fluorescence emission was “turned ON” in the presence of Hg2 + employed as a test analyte. The mechanism of the “turn ON” of the GQDs emission in the nanoconjugates is ascribed to the strong affinity of Hg2 + to bind with the bridging sulfur on the Pcs periphery thereby disrupting the π-π stacking interaction between the GQDs and the Pcs with a consequent “turn ON” of the coordinated GQDs' fluorescence.
- Full Text:
- Date Issued: 2017
Graphene quantum dots anchored onto mercaptopyridine-substituted zinc phthalocyanine-Au@ Ag nanoparticle hybrid: Application as fluorescence “off-on-off” sensor for Hg2+ and biothiols
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188194 , vital:44731 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.06.002"
- Description: Novel supramolecular hybrid containing polyethyleneimine-functionalized graphene quantum dots (PEI-GQDs) and mercaptopyridine-substituted zinc phthalocyanine (Pc)-Au@Ag nano-alloys is presented in this study. The designed hybrid was employed as a dual fluorescence nanoprobe for Hg2+ and biothiol detection in aqueous solution using PEI-GQDs as the fluorescence switching signal probe. The dual sensing platform for the analytes detection is firstly, based on the quenching (turn “OFF”) of the PEI-GQDs fluorescence upon π-π interaction or electrostatic attraction with Pc-Au@Ag conjugate. The quenched fluorescence can be switched back to the “ON” mode in the presence of Hg2+ and switched “OFF” again when biothiols are introduced to capture the Hg2+ ion via the formation of the strong metal-thiol bond (Hg-S). The “off-on-off” processes were modulated by different amounts of Hg2+ and biothiols. The nanoprobes were found to be highly stable and selective towards the target analytes in the presence of other amino acids and metal ions. Also, the probes were successfully deployed in the assay of the test analytes in spiked samples.
- Full Text:
- Date Issued: 2017
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188194 , vital:44731 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.06.002"
- Description: Novel supramolecular hybrid containing polyethyleneimine-functionalized graphene quantum dots (PEI-GQDs) and mercaptopyridine-substituted zinc phthalocyanine (Pc)-Au@Ag nano-alloys is presented in this study. The designed hybrid was employed as a dual fluorescence nanoprobe for Hg2+ and biothiol detection in aqueous solution using PEI-GQDs as the fluorescence switching signal probe. The dual sensing platform for the analytes detection is firstly, based on the quenching (turn “OFF”) of the PEI-GQDs fluorescence upon π-π interaction or electrostatic attraction with Pc-Au@Ag conjugate. The quenched fluorescence can be switched back to the “ON” mode in the presence of Hg2+ and switched “OFF” again when biothiols are introduced to capture the Hg2+ ion via the formation of the strong metal-thiol bond (Hg-S). The “off-on-off” processes were modulated by different amounts of Hg2+ and biothiols. The nanoprobes were found to be highly stable and selective towards the target analytes in the presence of other amino acids and metal ions. Also, the probes were successfully deployed in the assay of the test analytes in spiked samples.
- Full Text:
- Date Issued: 2017
Photophysical properties of a series of alloyed and non-alloyed water-soluble l-cysteine-capped core quantum dots
- Adegoke, Oluwasesan, Nyokong, Tebello, Forbes, Patricia B
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188486 , vital:44758 , xlink:href="https://doi.org/10.1016/j.jallcom.2016.10.276"
- Description: Photophysical properties of quantum dots (QDs) such as their photoluminescence (PL) quantum yield (QY), exciton lifetime and PL stability are important parameters used to unravel their chemical and physical characteristics. In this work, we have comparatively investigated the photophysical properties of a series of L-cysteine-capped non-alloyed (CdTe and CdSe) and alloyed (CdZnTe, CdSeS, CdSeTe and CdSeTeS) core QDs. Each of the QDs varied in their size and PL emission wavelength. We observe no physical relationship between the PL QY of the QDs and their PL stability. Based on the PL stability assessment, CdTe QDs with a high PL QY value of 88% exhibited poor PL stability while moderate PL stability was observed for CdZnTe (QY = 78%); CdSe (QY = 3%); and CdSeTe QDs (QY = ∼3%). Alloyed CdSeS (QY = ∼69%) and CdSeTeS (QY = 23%) QDs exhibited good PL stability and can serve as potential fluorophores for a wide range of chemical and biological applications. Generally, it is proposed that the structural nature of the QDs played a significant role in their overall photophysical properties. The information provided in this work will assist in the selection of core QDs suitable for different applications.
- Full Text:
- Date Issued: 2017
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188486 , vital:44758 , xlink:href="https://doi.org/10.1016/j.jallcom.2016.10.276"
- Description: Photophysical properties of quantum dots (QDs) such as their photoluminescence (PL) quantum yield (QY), exciton lifetime and PL stability are important parameters used to unravel their chemical and physical characteristics. In this work, we have comparatively investigated the photophysical properties of a series of L-cysteine-capped non-alloyed (CdTe and CdSe) and alloyed (CdZnTe, CdSeS, CdSeTe and CdSeTeS) core QDs. Each of the QDs varied in their size and PL emission wavelength. We observe no physical relationship between the PL QY of the QDs and their PL stability. Based on the PL stability assessment, CdTe QDs with a high PL QY value of 88% exhibited poor PL stability while moderate PL stability was observed for CdZnTe (QY = 78%); CdSe (QY = 3%); and CdSeTe QDs (QY = ∼3%). Alloyed CdSeS (QY = ∼69%) and CdSeTeS (QY = 23%) QDs exhibited good PL stability and can serve as potential fluorophores for a wide range of chemical and biological applications. Generally, it is proposed that the structural nature of the QDs played a significant role in their overall photophysical properties. The information provided in this work will assist in the selection of core QDs suitable for different applications.
- Full Text:
- Date Issued: 2017
One size does not fit all: Critical insights for effective community-based resource management in Melanesia
- Aswani, Shankar, Albert, Simon, Love, Mark
- Authors: Aswani, Shankar , Albert, Simon , Love, Mark
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/420459 , vital:71745 , xlink:href="http://dx.doi.org/10.1016/j.marpol.2017.03.041"
- Description: In recent years, Fiji's approach of combining traditional systems of community-based coastal management and modern management systems has become a successful blueprint for marine conservation, particularly the Locally Managed Marine Area (LMMA) network model. As a result of this success, conservation practitioners have imported the Fiji LMMA model to the Solomon Islands and in Vanuatu in hope of replicating the purported success attained in Fiji. This paper argues that because tenure systems and associated political systems in Fiji, the Solomon Islands, and Vanuatu are substantially different, one cannot simply extrapolate the more centralized tenurial and political Fiji model to the decentralized tenurial and politically eclectic Solomons and Vanuatu. This paper provides an analysis of some of the various approaches used in these countries to make a case for why socio-political diversity and historical particulars matter to resource management and conservation-in-practice (and for any development interventions). By examining examples of various nested and polycentric governance approaches—family, community, tribal, confederations, local community-based organizations (CBOs), and Church—it elucidate not only some of the differences between Fiji and Solomon Islands/Vanuatu, but also between Vanuatu and the Solomon Islands. This provides critical insights into some of the myriad of factors impinging on conservation aspirations in these countries and may offer some alternative ways forward not currently considered by conservation practitioners. Finally, the paper provides some guidelines to how to increase the long-term success of marine conservation programs for fisheries management and community-based management initiatives in the region.
- Full Text:
- Date Issued: 2017
- Authors: Aswani, Shankar , Albert, Simon , Love, Mark
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/420459 , vital:71745 , xlink:href="http://dx.doi.org/10.1016/j.marpol.2017.03.041"
- Description: In recent years, Fiji's approach of combining traditional systems of community-based coastal management and modern management systems has become a successful blueprint for marine conservation, particularly the Locally Managed Marine Area (LMMA) network model. As a result of this success, conservation practitioners have imported the Fiji LMMA model to the Solomon Islands and in Vanuatu in hope of replicating the purported success attained in Fiji. This paper argues that because tenure systems and associated political systems in Fiji, the Solomon Islands, and Vanuatu are substantially different, one cannot simply extrapolate the more centralized tenurial and political Fiji model to the decentralized tenurial and politically eclectic Solomons and Vanuatu. This paper provides an analysis of some of the various approaches used in these countries to make a case for why socio-political diversity and historical particulars matter to resource management and conservation-in-practice (and for any development interventions). By examining examples of various nested and polycentric governance approaches—family, community, tribal, confederations, local community-based organizations (CBOs), and Church—it elucidate not only some of the differences between Fiji and Solomon Islands/Vanuatu, but also between Vanuatu and the Solomon Islands. This provides critical insights into some of the myriad of factors impinging on conservation aspirations in these countries and may offer some alternative ways forward not currently considered by conservation practitioners. Finally, the paper provides some guidelines to how to increase the long-term success of marine conservation programs for fisheries management and community-based management initiatives in the region.
- Full Text:
- Date Issued: 2017
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
Understanding spatial variation in the drivers of nature-based tourism and their influence on the sustainability of private land conservation
- Baum, Julia, Cumming, Graeme S, de Vos, Alta
- Authors: Baum, Julia , Cumming, Graeme S , de Vos, Alta
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416481 , vital:71352 , xlink:href="https://doi.org/10.1016/j.ecolecon.2017.05.005"
- Description: Protected areas connect socio-economic and ecological systems through their provision of ecosystem goods and services. Analysis of ecosystem services allows the expression of ecological benefits in economic terms. However, cultural services, such as recreation opportunities, have proved difficult to quantify. An important challenge for the analysis of cultural services is to understand the geography of service provision in relation to both human and ecological system elements. We used data on visitation rates and measures of context, content, connectivity, and location for 64 private land conservation areas (PLCAs) to better understand geographic influences on cultural service provision. Visitation to PLCAs was influenced by a combination of ecological and socio-economic drivers. Variance partitioning analysis showed that ecology explained the largest proportion of overall variation in visitation rates (26%), followed by location (22%). In tests using generalized linear mixed models, individual factors that significantly explained visitation rates included the number of mammal species, the number of Big 5-species (ecological variables), the number of facilities provided (infrastructure) and average accommodation charges (affordability). Our analysis has important implications for the economic sustainability of PLCAs and more generally for understanding the relevance of spatial variation for analyses of cultural services.
- Full Text:
- Date Issued: 2017
- Authors: Baum, Julia , Cumming, Graeme S , de Vos, Alta
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416481 , vital:71352 , xlink:href="https://doi.org/10.1016/j.ecolecon.2017.05.005"
- Description: Protected areas connect socio-economic and ecological systems through their provision of ecosystem goods and services. Analysis of ecosystem services allows the expression of ecological benefits in economic terms. However, cultural services, such as recreation opportunities, have proved difficult to quantify. An important challenge for the analysis of cultural services is to understand the geography of service provision in relation to both human and ecological system elements. We used data on visitation rates and measures of context, content, connectivity, and location for 64 private land conservation areas (PLCAs) to better understand geographic influences on cultural service provision. Visitation to PLCAs was influenced by a combination of ecological and socio-economic drivers. Variance partitioning analysis showed that ecology explained the largest proportion of overall variation in visitation rates (26%), followed by location (22%). In tests using generalized linear mixed models, individual factors that significantly explained visitation rates included the number of mammal species, the number of Big 5-species (ecological variables), the number of facilities provided (infrastructure) and average accommodation charges (affordability). Our analysis has important implications for the economic sustainability of PLCAs and more generally for understanding the relevance of spatial variation for analyses of cultural services.
- Full Text:
- Date Issued: 2017
Effects of symmetry and the number of positive charges on the photocatalytic activity of indium phthalocyanines when embedded in electrospun fibers
- Chakona, Gamuchirai, Nyokong, Tebello
- Authors: Chakona, Gamuchirai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188304 , vital:44743 , xlink:href="https://doi.org/10.1016/j.ica.2016.12.025"
- Description: Photooxidations of bisphenol A and 4-chlorophenol were carried out in this study using two asymmetric indium(III) phthalocyanines photosensitizers: the first consisting of one quaternized 4-pyridyloxyl and no other substituents (complex 1) and the second containing three quaternized 4-pyridylsulfanyl units and one aminophenoxy (complex 3). The asymmetry of complex 3 is additionally caused by the presence of two linking atoms (O and S). The symmetrically substituted indium(III) phthalocyanine containing four quaternized 4-pyridyloxyl units (complex 2) was also studied. The complexes were embedded in electrospun polystyrene fiber for heterogeneous photocatalytic transformation of 4-chlorophenol and bisphenol A. When immobilized on electrospun fibers, complexes 1, 2 and 3 gave singlet oxygen values of 0.31, 0.39 and 0.50 in water, respectively. Complex 3 showed the best photocatalytic behavior with observed rate constants of 2.8 × 10−3 min−1 for bisphenol A and 3.8 × 10−3 min−1 for 4-chlorophenol.
- Full Text:
- Date Issued: 2017
- Authors: Chakona, Gamuchirai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188304 , vital:44743 , xlink:href="https://doi.org/10.1016/j.ica.2016.12.025"
- Description: Photooxidations of bisphenol A and 4-chlorophenol were carried out in this study using two asymmetric indium(III) phthalocyanines photosensitizers: the first consisting of one quaternized 4-pyridyloxyl and no other substituents (complex 1) and the second containing three quaternized 4-pyridylsulfanyl units and one aminophenoxy (complex 3). The asymmetry of complex 3 is additionally caused by the presence of two linking atoms (O and S). The symmetrically substituted indium(III) phthalocyanine containing four quaternized 4-pyridyloxyl units (complex 2) was also studied. The complexes were embedded in electrospun polystyrene fiber for heterogeneous photocatalytic transformation of 4-chlorophenol and bisphenol A. When immobilized on electrospun fibers, complexes 1, 2 and 3 gave singlet oxygen values of 0.31, 0.39 and 0.50 in water, respectively. Complex 3 showed the best photocatalytic behavior with observed rate constants of 2.8 × 10−3 min−1 for bisphenol A and 3.8 × 10−3 min−1 for 4-chlorophenol.
- Full Text:
- Date Issued: 2017
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
The relevance of cross-scale connections and spatial interactions for ecosystem service delivery by protected areas: Insights from southern Africa
- de Vos, Alta, Cumming, Graeme S, Roux, Dirk J
- Authors: de Vos, Alta , Cumming, Graeme S , Roux, Dirk J
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416438 , vital:71348 , xlink:href="https://doi.org/10.1016/j.ecoser.2017.11.014"
- Description: The ecosystem services (ES) concept can frame the value of protected areas (PAs) to society and identify management actions that bridge biodiversity conservation and human benefits. In this special issue on ES flows to and from southern African PAs we consider two themes: (1) water as a biophysical and social-ecological connector; and (2) cross-scale interactions and connections as influences on cultural ecosystem service (CES) provision. Freshwater flows have supporting, regulating, and cultural elements, leading to complexities in governance as well as place attachment, intellectual, and recreational services. Scale dependence in CES creates trade-offs that challenge the usefulness of the ES framework for PA management. Ecosystem service production can potentially create political support for PAs and helps to build connections and feedbacks that increase PA resilience. Papers in the feature highlight a need to understand trade-offs in optimising for biodiversity vs. particular bundles of ES; impacts of investment in built infrastructure on ES use; how managers facilitate ES; scale and heterogeneity as influences; the role of adaptive monitoring of PAs as social–ecological systems; and services and benefits from PAs that are not well-articulated in ES classifications. PA research can thus add nuance, depth and substance to broader thinking around CES.
- Full Text:
- Date Issued: 2017
- Authors: de Vos, Alta , Cumming, Graeme S , Roux, Dirk J
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416438 , vital:71348 , xlink:href="https://doi.org/10.1016/j.ecoser.2017.11.014"
- Description: The ecosystem services (ES) concept can frame the value of protected areas (PAs) to society and identify management actions that bridge biodiversity conservation and human benefits. In this special issue on ES flows to and from southern African PAs we consider two themes: (1) water as a biophysical and social-ecological connector; and (2) cross-scale interactions and connections as influences on cultural ecosystem service (CES) provision. Freshwater flows have supporting, regulating, and cultural elements, leading to complexities in governance as well as place attachment, intellectual, and recreational services. Scale dependence in CES creates trade-offs that challenge the usefulness of the ES framework for PA management. Ecosystem service production can potentially create political support for PAs and helps to build connections and feedbacks that increase PA resilience. Papers in the feature highlight a need to understand trade-offs in optimising for biodiversity vs. particular bundles of ES; impacts of investment in built infrastructure on ES use; how managers facilitate ES; scale and heterogeneity as influences; the role of adaptive monitoring of PAs as social–ecological systems; and services and benefits from PAs that are not well-articulated in ES classifications. PA research can thus add nuance, depth and substance to broader thinking around CES.
- Full Text:
- Date Issued: 2017
Investigation of photophysicochemical properties of zinc phthalocyanines conjugated to metallic nanoparticles
- Dube, Edith, Nwaji, Njemuwa, Oluwole, David O, Mack, John, Nyokong, Tebello
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2017
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2017
Photophysicochemical behaviour of anionic indium phthalocyanine when grafted onto AgxAuy and porous silica nanoparticles
- Dube, Edith, Oluwole, David O, Nyokong, Tebello
- Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188899 , vital:44796 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.05.071"
- Description: This work reports on the synthesis of glutathione functionalised Ag3Au1 (Ag rich alloy, denoted as AgAu) and Ag1Au3 (Au rich alloy – denoted as AuAg) nano alloys as well as aminopropyl triethoxylsilane capped Ag1Au3 doped silica nanoparticles (NPs). The NPs were covalently linked to indium(III) chloride 2,9(10),16(17),23(24)–tetra–(3–carboxyphenoxy)phthalocyanine (1) via amide bond to form 1–AgAuNPs–GSH and 1–AuAgNPs–GSH. The AgAuNPs were also doped into aminopropyl triethoxylsilane (APTES) silica NPs (SiNPs-APTES) followed by linkage to complex 1 to form 1–AgAu-SiNPs–APTES. The photophysicochemical behaviour of complex 1 and its nanoconjugates were investigated. Decrease in the fluorescence quantum yields and lifetimes was observed in the conjugates in comparison to 1 alone. The singlet oxygen quantum yield for 1–AgAuNPs–GSH and 1–AuAgNPs–GSH decreased probably due to the screening effect caused by the NPs, while that of 1–AgAu-SiNPs–APTES increased in dimethylsulfoxide probably due to the permeability of the porous silica matrix to molecular oxygen.
- Full Text:
- Date Issued: 2017
- Authors: Dube, Edith , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188899 , vital:44796 , xlink:href="https://doi.org/10.1016/j.jlumin.2017.05.071"
- Description: This work reports on the synthesis of glutathione functionalised Ag3Au1 (Ag rich alloy, denoted as AgAu) and Ag1Au3 (Au rich alloy – denoted as AuAg) nano alloys as well as aminopropyl triethoxylsilane capped Ag1Au3 doped silica nanoparticles (NPs). The NPs were covalently linked to indium(III) chloride 2,9(10),16(17),23(24)–tetra–(3–carboxyphenoxy)phthalocyanine (1) via amide bond to form 1–AgAuNPs–GSH and 1–AuAgNPs–GSH. The AgAuNPs were also doped into aminopropyl triethoxylsilane (APTES) silica NPs (SiNPs-APTES) followed by linkage to complex 1 to form 1–AgAu-SiNPs–APTES. The photophysicochemical behaviour of complex 1 and its nanoconjugates were investigated. Decrease in the fluorescence quantum yields and lifetimes was observed in the conjugates in comparison to 1 alone. The singlet oxygen quantum yield for 1–AgAuNPs–GSH and 1–AuAgNPs–GSH decreased probably due to the screening effect caused by the NPs, while that of 1–AgAu-SiNPs–APTES increased in dimethylsulfoxide probably due to the permeability of the porous silica matrix to molecular oxygen.
- Full Text:
- Date Issued: 2017
Population size and development history determine street tree distribution and composition within and between Eastern Cape towns, South Africa
- Gwedla, Nanamhla, Shackleton, Charlie M
- Authors: Gwedla, Nanamhla , Shackleton, Charlie M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180468 , vital:43392 , xlink:href="https://doi.org/10.1016/j.ufug.2017.04.014"
- Description: Street trees are a common feature of urban nature, providing ecological, economic and social benefits. These public functions are highly dependent on specific design principles, including the composition and diversity of tree species within the urban forest. Consequently, it is important to understand the patterns and correlates of street tree distribution and diversity to assess benefit flows. This requires sampling across and within towns. This paper reports on an assessment of the distribution, composition and diversity of street trees between and within multiple South African towns, and ascertains the correlations between tree density and composition with social contexts. Randomly selected streets were sampled in the affluent, township and low cost housing suburbs of ten Eastern Cape towns. Sixty-nine out of 300 sampled transects had street trees, with 888 trees enumerated, spanning 97 species. Alien tree species accounted for 71% of all the enumerated trees while indigenous trees species accounted for 12%. Tree density and composition were significantly lower in smaller towns and those marginalised during the previous racially-based political regime. Within towns, the poor areas had fewer street trees, with many streets having none. Collaboration and constant communication between the various government departments involved in suburb development is crucial to ensure a more rigorous incorporation of green infrastructure into the building and development plans of new housing developments.
- Full Text:
- Date Issued: 2017
- Authors: Gwedla, Nanamhla , Shackleton, Charlie M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180468 , vital:43392 , xlink:href="https://doi.org/10.1016/j.ufug.2017.04.014"
- Description: Street trees are a common feature of urban nature, providing ecological, economic and social benefits. These public functions are highly dependent on specific design principles, including the composition and diversity of tree species within the urban forest. Consequently, it is important to understand the patterns and correlates of street tree distribution and diversity to assess benefit flows. This requires sampling across and within towns. This paper reports on an assessment of the distribution, composition and diversity of street trees between and within multiple South African towns, and ascertains the correlations between tree density and composition with social contexts. Randomly selected streets were sampled in the affluent, township and low cost housing suburbs of ten Eastern Cape towns. Sixty-nine out of 300 sampled transects had street trees, with 888 trees enumerated, spanning 97 species. Alien tree species accounted for 71% of all the enumerated trees while indigenous trees species accounted for 12%. Tree density and composition were significantly lower in smaller towns and those marginalised during the previous racially-based political regime. Within towns, the poor areas had fewer street trees, with many streets having none. Collaboration and constant communication between the various government departments involved in suburb development is crucial to ensure a more rigorous incorporation of green infrastructure into the building and development plans of new housing developments.
- 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
A2B type copper (III) corroles containing zero-to-five fluorine atoms
- Li, Minzhi, Niu, Yingjie, Zhu, Weihua, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Liang, Xu
- Authors: Li, Minzhi , Niu, Yingjie , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238275 , vital:50604 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.10.044"
- Description: Four low symmetric A2B meso-substituted Cu(III)corroles with electron withdrawing meso-aryl rings have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to a series of DFT and TD-DFT calculations. A series of experiments demonstrate that these Cu(III)corroles can be used as highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, when the number of fluorine atoms at B meso-position is increased, there is a marked enhancement in the catalytic ability of the corrole complexes, which demonstrates that modification to the structures of low symmetry corroles is a useful strategy for developing new HER catalysts.
- Full Text:
- Date Issued: 2017
- Authors: Li, Minzhi , Niu, Yingjie , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238275 , vital:50604 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.10.044"
- Description: Four low symmetric A2B meso-substituted Cu(III)corroles with electron withdrawing meso-aryl rings have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to a series of DFT and TD-DFT calculations. A series of experiments demonstrate that these Cu(III)corroles can be used as highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, when the number of fluorine atoms at B meso-position is increased, there is a marked enhancement in the catalytic ability of the corrole complexes, which demonstrates that modification to the structures of low symmetry corroles is a useful strategy for developing new HER catalysts.
- Full Text:
- Date Issued: 2017
Highly efficient CCl bond cleavage and unprecedented CC bond cleavage of environmentally toxic DDT through molecular electrochemical catalysis
- Liang, Xu, Huang, Tingting, Li, Minzhi, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Date Issued: 2017
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Date Issued: 2017
Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol
- Makinde, Zainab O, Louzada, Marcel, Mashazi, Philani N, Nyokong, Tebello, Khene, Samson M
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
- Full Text:
- Date Issued: 2017
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
- Full Text:
- Date Issued: 2017
The photophysical studies of Pluronic F127/P123 micelle mixture system loaded with metal free and Zn 5, 10, 15, 20-tetrakis [4-(benzyloxy) phenyl] porphyrins
- Managa, Muthumuni, Ngoy, Bokolombe P, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188932 , vital:44799 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.02.018"
- Description: Binary mixtures of Pluronics are studied as drug nanocarriers in this work. H2 and Zn 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin were encapsulated onto binary micelle mixture of Pluronic F127/P123. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence quantum yield for H2TBnOPP (ΦF = 0.034) was higher than that of ZnTBnOPP (ΦF = 0.023) and decreased when ZnTBnOPP or H2TBnOPP when in the presence of Pluronic F127/P123 binary mixtures. The kq values were 2.8 × 108 and 3.7 × 108 M−1 s−1, for H2TBnOPP + Pluronic F127/P123 and ZnTBnOPP + Pluronic F127/P123 in water, respectively. The binding constants (Kb) were 1.58 × 105 M−1 and 1.02 × 105 M−1 for ZnTBnOPP + Pluronic F127/P123 and H2TBnOPP + Pluronic F127/P123, respectively.
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188932 , vital:44799 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.02.018"
- Description: Binary mixtures of Pluronics are studied as drug nanocarriers in this work. H2 and Zn 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin were encapsulated onto binary micelle mixture of Pluronic F127/P123. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence quantum yield for H2TBnOPP (ΦF = 0.034) was higher than that of ZnTBnOPP (ΦF = 0.023) and decreased when ZnTBnOPP or H2TBnOPP when in the presence of Pluronic F127/P123 binary mixtures. The kq values were 2.8 × 108 and 3.7 × 108 M−1 s−1, for H2TBnOPP + Pluronic F127/P123 and ZnTBnOPP + Pluronic F127/P123 in water, respectively. The binding constants (Kb) were 1.58 × 105 M−1 and 1.02 × 105 M−1 for ZnTBnOPP + Pluronic F127/P123 and H2TBnOPP + Pluronic F127/P123, respectively.
- Full Text:
- Date Issued: 2017
Photophysical properties of GaCl 5, 10, 15, 20-tetra (1-pyrenyl) porphyrinato incorporated into Pluronic F127 micelle
- Managa, Muthumuni, Britton, Jonathan, Amuhaya, Edith K, Nyokong, Tebello
- Authors: Managa, Muthumuni , Britton, Jonathan , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233101 , vital:50056 , xlink:href="https://doi.org/10.1016/j.jlumin.2016.12.043"
- Description: GaCl 5,10,15,20-Tetra(1-pyrenyl)porphyrin (GaClTPyP) was successfully synthesised and encapsulated into Pluronic F127. The unmetallated 5,10,15,20-tetra(1-pyrenyl)porphyrin (H2TPyP) precursor was also encapsulated into Pluronic F127. The fluorescence quantum yield for GaClTPyP at 0.045 was lower than that of H2TPyP at 0.13 due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state, lowering the fluorescence. Fluorescence quantum yield values increased when GaClTPyP or H2TPyP were encapsulated in Pluronic F127. GaClTPyP/Pluronic F127 showed higher values of the binding constant (Kb) as well as Stern-Volmer constant (Ksv) when compared to H2ClTPyP/Pluronic F127. It was determined from fluorescence quenching studies for GaClTPyP was located more in the inner core (hydrophobic) of Pluronic F127 and H2TPyP more on the outer region. Single oxygen quantum yields (Ф△) were determined to be 0.32 and 0.53 for GaClTPyP and GaClTPyP/Pluronic F127 respectively, an increase for the latter compared to the former.
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Britton, Jonathan , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233101 , vital:50056 , xlink:href="https://doi.org/10.1016/j.jlumin.2016.12.043"
- Description: GaCl 5,10,15,20-Tetra(1-pyrenyl)porphyrin (GaClTPyP) was successfully synthesised and encapsulated into Pluronic F127. The unmetallated 5,10,15,20-tetra(1-pyrenyl)porphyrin (H2TPyP) precursor was also encapsulated into Pluronic F127. The fluorescence quantum yield for GaClTPyP at 0.045 was lower than that of H2TPyP at 0.13 due to the heavy atom effect of Ga in the former which encourages intersystem crossing to the triplet state, lowering the fluorescence. Fluorescence quantum yield values increased when GaClTPyP or H2TPyP were encapsulated in Pluronic F127. GaClTPyP/Pluronic F127 showed higher values of the binding constant (Kb) as well as Stern-Volmer constant (Ksv) when compared to H2ClTPyP/Pluronic F127. It was determined from fluorescence quenching studies for GaClTPyP was located more in the inner core (hydrophobic) of Pluronic F127 and H2TPyP more on the outer region. Single oxygen quantum yields (Ф△) were determined to be 0.32 and 0.53 for GaClTPyP and GaClTPyP/Pluronic F127 respectively, an increase for the latter compared to the former.
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- Date Issued: 2017